US6423326B1 - Cold-mix water-in-oil emulsions comprising quaternary ammonium compounds and process for producing same - Google Patents
Cold-mix water-in-oil emulsions comprising quaternary ammonium compounds and process for producing same Download PDFInfo
- Publication number
- US6423326B1 US6423326B1 US09/627,783 US62778300A US6423326B1 US 6423326 B1 US6423326 B1 US 6423326B1 US 62778300 A US62778300 A US 62778300A US 6423326 B1 US6423326 B1 US 6423326B1
- Authority
- US
- United States
- Prior art keywords
- cold
- water
- oil
- oil emulsion
- emulsifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims abstract description 167
- 239000000839 emulsion Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 44
- 150000003856 quaternary ammonium compounds Chemical class 0.000 title 1
- 239000003974 emollient agent Substances 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 50
- 239000007957 coemulsifier Substances 0.000 claims abstract description 41
- 238000004945 emulsification Methods 0.000 claims abstract description 20
- 239000012071 phase Substances 0.000 claims description 120
- 239000003921 oil Substances 0.000 claims description 73
- 239000007762 w/o emulsion Substances 0.000 claims description 58
- 238000013019 agitation Methods 0.000 claims description 51
- -1 alcohol ester Chemical class 0.000 claims description 44
- 235000019198 oils Nutrition 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 21
- 229940008099 dimethicone Drugs 0.000 claims description 19
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 239000008346 aqueous phase Substances 0.000 claims description 14
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical group OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 12
- 229940085262 cetyl dimethicone Drugs 0.000 claims description 11
- 150000001280 alpha hydroxy acids Chemical class 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 229940061720 alpha hydroxy acid Drugs 0.000 claims description 8
- 150000001277 beta hydroxy acids Chemical class 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 6
- 229940120503 dihydroxyacetone Drugs 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229940086555 cyclomethicone Drugs 0.000 claims description 5
- BANXPJUEBPWEOT-UHFFFAOYSA-N 2-methyl-Pentadecane Chemical compound CCCCCCCCCCCCCC(C)C BANXPJUEBPWEOT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 235000019486 Sunflower oil Nutrition 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000015096 spirit Nutrition 0.000 claims description 3
- 239000002600 sunflower oil Substances 0.000 claims description 3
- 229940043268 2,2,4,4,6,8,8-heptamethylnonane Drugs 0.000 claims description 2
- ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 2-dodecanoyloxyethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCC ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 0.000 claims description 2
- CMBYOWLFQAFZCP-UHFFFAOYSA-N Hexyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCCCC CMBYOWLFQAFZCP-UHFFFAOYSA-N 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 2
- 229940100463 hexyl laurate Drugs 0.000 claims description 2
- KUVMKLCGXIYSNH-UHFFFAOYSA-N isopentadecane Natural products CCCCCCCCCCCCC(C)C KUVMKLCGXIYSNH-UHFFFAOYSA-N 0.000 claims description 2
- 229940119170 jojoba wax Drugs 0.000 claims description 2
- 229940070765 laurate Drugs 0.000 claims description 2
- 229940100518 polyglyceryl-4 isostearate Drugs 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims 2
- 125000005457 triglyceride group Chemical group 0.000 claims 2
- 239000000516 sunscreening agent Substances 0.000 abstract description 58
- 230000000475 sunscreen effect Effects 0.000 abstract description 48
- 239000006210 lotion Substances 0.000 abstract description 16
- 239000002537 cosmetic Substances 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000000499 gel Substances 0.000 abstract description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 5
- 239000007921 spray Substances 0.000 abstract description 5
- 210000003491 skin Anatomy 0.000 description 28
- 239000004615 ingredient Substances 0.000 description 22
- 238000009472 formulation Methods 0.000 description 15
- 229920001296 polysiloxane Polymers 0.000 description 15
- 239000003755 preservative agent Substances 0.000 description 14
- 230000003750 conditioning effect Effects 0.000 description 13
- 239000003205 fragrance Substances 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 12
- 239000003085 diluting agent Substances 0.000 description 12
- 0 *C(=O)OC(C)CN(CCN(C)(CC(C)O)CC(C)O)CC(C)OC(*)=O.COS(=O)(=O)[O-] Chemical compound *C(=O)OC(C)CN(CCN(C)(CC(C)O)CC(C)O)CC(C)OC(*)=O.COS(=O)(=O)[O-] 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 150000003868 ammonium compounds Chemical group 0.000 description 11
- 239000003906 humectant Substances 0.000 description 11
- 230000002335 preservative effect Effects 0.000 description 11
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- OQILCOQZDHPEAZ-UHFFFAOYSA-N octyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OCCCCCCCC OQILCOQZDHPEAZ-UHFFFAOYSA-N 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 150000002194 fatty esters Chemical class 0.000 description 5
- WCJLCOAEJIHPCW-UHFFFAOYSA-N octyl 2-hydroxybenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1O WCJLCOAEJIHPCW-UHFFFAOYSA-N 0.000 description 5
- QXVUGSHEKWUGTL-UHFFFAOYSA-N octyl 2-methoxy-3-phenylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(OC)=CC1=CC=CC=C1 QXVUGSHEKWUGTL-UHFFFAOYSA-N 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 230000003020 moisturizing effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000037072 sun protection Effects 0.000 description 4
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 3
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- NGEWQZIDQIYUNV-UHFFFAOYSA-N L-valinic acid Natural products CC(C)C(O)C(O)=O NGEWQZIDQIYUNV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- BTNMPGBKDVTSJY-UHFFFAOYSA-N keto-phenylpyruvic acid Chemical compound OC(=O)C(=O)CC1=CC=CC=C1 BTNMPGBKDVTSJY-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007764 o/w emulsion Substances 0.000 description 3
- 229960001679 octinoxate Drugs 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- LADGBHLMCUINGV-UHFFFAOYSA-N tricaprin Chemical compound CCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC LADGBHLMCUINGV-UHFFFAOYSA-N 0.000 description 3
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- HWXBTNAVRSUOJR-UHFFFAOYSA-N 2-hydroxyglutaric acid Chemical compound OC(=O)C(O)CCC(O)=O HWXBTNAVRSUOJR-UHFFFAOYSA-N 0.000 description 2
- 241000283153 Cetacea Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 2
- 239000004264 Petrolatum Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SASYSVUEVMOWPL-NXVVXOECSA-N decyl oleate Chemical compound CCCCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC SASYSVUEVMOWPL-NXVVXOECSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 229960002510 mandelic acid Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229960003921 octisalate Drugs 0.000 description 2
- YPMOZWCBANATQH-UHFFFAOYSA-N octyl 7-methyloctanoate Chemical compound CCCCCCCCOC(=O)CCCCCC(C)C YPMOZWCBANATQH-UHFFFAOYSA-N 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- 229960001173 oxybenzone Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 2
- 229960000368 sulisobenzone Drugs 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- PDHSAQOQVUXZGQ-JKSUJKDBSA-N (2r,3s)-2-(3,4-dihydroxyphenyl)-3-methoxy-3,4-dihydro-2h-chromene-5,7-diol Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2OC)=CC=C(O)C(O)=C1 PDHSAQOQVUXZGQ-JKSUJKDBSA-N 0.000 description 1
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 1
- LVRFTAZAXQPQHI-RXMQYKEDSA-N (R)-2-hydroxy-4-methylpentanoic acid Chemical compound CC(C)C[C@@H](O)C(O)=O LVRFTAZAXQPQHI-RXMQYKEDSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 1
- ABEXEQSGABRUHS-UHFFFAOYSA-N 16-methylheptadecyl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC(C)C ABEXEQSGABRUHS-UHFFFAOYSA-N 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N 2,2,4,6,6-pentamethylheptane Chemical compound CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- DGSZGZSCHSQXFV-UHFFFAOYSA-N 2,3-bis(2-ethylhexanoyloxy)propyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(OC(=O)C(CC)CCCC)COC(=O)C(CC)CCCC DGSZGZSCHSQXFV-UHFFFAOYSA-N 0.000 description 1
- LOUGYXZSURQALL-UHFFFAOYSA-N 2,3-dihydroxybutanoic acid Chemical compound CC(O)C(O)C(O)=O LOUGYXZSURQALL-UHFFFAOYSA-N 0.000 description 1
- SODSBJHVKSGOIZ-UHFFFAOYSA-N 2-Amino-3,4-dihydroxypentanedioic acid Chemical compound OC(=O)C(N)C(O)C(O)C(O)=O SODSBJHVKSGOIZ-UHFFFAOYSA-N 0.000 description 1
- OPJWPPVYCOPDCM-UHFFFAOYSA-N 2-ethylhexyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)CCCC OPJWPPVYCOPDCM-UHFFFAOYSA-N 0.000 description 1
- MBIQENSCDNJOIY-UHFFFAOYSA-N 2-hydroxy-2-methylbutyric acid Chemical compound CCC(C)(O)C(O)=O MBIQENSCDNJOIY-UHFFFAOYSA-N 0.000 description 1
- VHBSECWYEFJRNV-UHFFFAOYSA-N 2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1O.OC(=O)C1=CC=CC=C1O VHBSECWYEFJRNV-UHFFFAOYSA-N 0.000 description 1
- AFENDNXGAFYKQO-UHFFFAOYSA-N 2-hydroxybutyric acid Chemical compound CCC(O)C(O)=O AFENDNXGAFYKQO-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- SGRCVQDBWHCTIS-UHFFFAOYSA-N 2-nonanoyloxypropyl nonanoate Chemical compound CCCCCCCCC(=O)OCC(C)OC(=O)CCCCCCCC SGRCVQDBWHCTIS-UHFFFAOYSA-N 0.000 description 1
- 239000001903 2-oxo-3-phenylpropanoic acid Substances 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/416—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/04—Preparations for care of the skin for chemically tanning the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/28—Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
Definitions
- the present invention relates to stable cold-mix water-in-oil emulsions and methods for preparing such emulsions. More specifically, the invention relates to cold-mix water-in-oil emulsions comprising oil (i.e., an emollient), water and an emulsification system comprising a quaternary ammonium-based low HLB emulsifier and optional co-emulsifiers.
- the present invention relates to cosmetic compositions which contain the inventive cold-mix oil and water emulsions. These cosmetic compositions are typically in the form of lotions, gels, or sprays, which provide improved moisturization, skin feel, skin care, and appearance benefits and reduced greasiness, together with excellent rub-in and absorption characteristics.
- the instant invention also relates to cold-mix water-in-oil sunscreen emulsions and methods for preparing such sunscreen emulsions.
- the emulsions of the instant invention generally display excellent extended duration stability characteristics at both normal and elevated
- water-in-oil compositions are well known, they are difficult to prepare as they normally require heating to high temperatures (i.e., greater than 50° C.) and generally have not enjoyed commercial success and/or consumer popularity due to unacceptable greasiness.
- the disadvantages of preparing water-in-oil emulsions at higher temperatures include promotion of unacceptable water loss through evaporation, time-consummation, inefficient processing, and the added processing expense of heating the emulsion.
- compositions of the instant invention can be prepared with little to no heat, i.e., they are prepared as a water-in-oil emulsion which is capable of being substantially completely emulsified and stable at about 25° C.
- these emulsions are stable, light and have a non-greasy feel when applied to the skin.
- the present invention provides skin-care cosmetic compositions which provide improved moisturization, absorption, skin feel, skin care and appearance characteristics and, which in particular, provide improved short and longer term moisturizing effectiveness, while at the same time reducing stickiness and avoiding a greasy feel on the skin.
- the compositions also display excellent stability characteristics at both normal and elevated temperatures.
- Another object of the invention is to provide cold-mix water-in-oil sunscreen emulsions comprising oil (i.e., an emollient), water, an emulsification system comprising a quaternary ammonium-based low HLB emulsifier and optional co-emulsifiers, and a sun screen agent.
- Another objection of the invention relates to bulk and finished cosmetic compositions (lotions, gels, sprays) which contain the inventive cold-mix water-in-oil emulsions and cold-mix water-in-oil sunscreen emulsions.
- the invention further relates to cold-mix methods of preparing the cold-mix water-in-oil emulsions disclosed, including the cold-mix water-in-oil sunscreen emulsions described herein.
- water-in-oil emulsions can be prepared as a cold mix water-in-oil emulsions at about 25° C.
- the present invention also encompasses cold mix water-in-oil sunscreen emulsions.
- the present invention encompasses a cold-mix water-in-oil emulsion comprising:
- R is substantially linear nor-oleyl
- the emulsification system and co-emulsifier substantially permanently maintaining the water and emollient as an emulsion, the emulsion capable of being substantially completely emulsified and stable at about 25° C.
- the present invention encompasses a cold-mix water-in-oil sunscreen emulsion comprising:
- R is substantially linear nor-oleyl
- the emulsification system and the co-emulsifier substantially permanently maintain the water and emollient as a sunscreen emulsion, the sunscreen emulsion capable of being substantially completely emulsified and stable at about 25° C.
- the invention also includes methods for making and using such emulsions.
- the emulsions described herein are primarily useful in finished sun screening formulations for application to human skin and in finished moisturizing creams, lotions, gels, and sprays for application to human skin.
- the inventive emulsions may be topically applied to human skin to moisturize the skin and/or may also be applied to human skin before prolonged exposure to light radiation to prevent the erythema normally observed after such exposure, i.e. the prevention of sun burn.
- the present invention encompasses novel cold-mix water-in-oil emulsions utilizing quaternary ammonium-based low HLB emulsifiers.
- the emulsions are readily prepared at low temperatures, i.e. at about 25° C.
- the emulsification system and the co-emulsifier substantially permanently maintain the water and emollient as a water-in-oil emulsion, where such emulsion is substantially completely emulsified and stable at about 25° C.; by this it is meant that the water-in-oil emulsion and/or water-in-oil sunscreen emulsion remains substantially completely emulsified and does not phase separate in two or more layers (e.g., a water layer and an oil layer) at 25° C. for a minimum of 14 days.
- layers e.g., a water layer and an oil layer
- the emulsions of the instant invention preferably contain sufficient amounts of ingredients that will produce an emulsion having a smooth, continuous appearance when emulsified.
- low HLB emulsifier as used herein means an emulsifier with an HLB below 12, and preferred HLB below 10.
- HLB Hydrophilic-Lipophilic Balance. HLB is a reflection of the balance between the lipophilic and hydrophilic moieties of a molecule (surfactant or emulsifier), such as the low HLB emulsifiers described herein.
- HLB Lipophilic and hydrophilic moieties of a molecule
- a lower HLB value indicates a more lipophilic surfactant, which is accordingly more oil-soluble.
- HLB values may be calculated by a variety of know methods to those skilled in the art. (See for example: Rosen, Surfactants and Interfacial Phenomena, 2 nd ed., Wiley Interscience, 1989.)
- the present invention encompasses a cold-mix water-in-oil emulsion comprising:
- R is substantially linear nor-oleyl
- the emulsification system and co-emulsifier substantially permanently maintaining the water and emollient as an emulsion, the emulsion capable of being substantially completely emulsified and stable at about 25° C. More preferably the cold-mix water-in-oil emulsion comprises from about 10% to about 30% by weight of the emollient, and most preferably from about 15% to about 25% by weight of the emollient.
- the cold-mix water-in-oil emulsion will comprise from about 0.5% to about 15% by weight of the low HLB emulsifier, more preferably from about 0.5% to about 8% by weight of the low HLB emulsifier, and most preferably from about 1% to about 3% by weight of the low HLB emulsifier.
- emollients are dimethicone, cyclomethicone, triglycerides, alcohol esters, ethoxylated esters, hydrocarbons, natural oils or a mixture thereof.
- the preferred hydrocarbon are mineral oil, mineral spirits, isohexadecane, or a mixture thereof.
- the most preferred emollients are triglycerides, alcohol esters, ethoxylated esters, glycol ethers, natural oils or a mixture thereof.
- preferred natural oils include safflower oil, jojoba oil, sunflower oil, or a mixture thereof.
- the cold-mix water-in-oil emulsion of the invention can additionally comprise a water-soluble nonionic surfactant.
- Preferred water-soluble nonionic surfactants are selected from the group consisting of polyethylene glycol laurate, polyethylene glycol dilaurate, or a mixture thereof.
- the cold-mix water-in-oil emulsion comprises from about 0.2% to about 22.5% by weight of the co-emulsifier, more preferably from about 0.2% to about 12.0% by weight of the co-emulsifier and most preferably from about 0.4% to about 4.5% by weight of the co-emulsifier.
- a preferred co-emulsifier is a dimethicone copolyol, selected from the group consisting of a cyclomethicone-dimethicone copolyol mixture, lauryl dimethicone copolyol, cetyl dimethicone copolyol, cetyl dimethicone copolyol/polyglyceryl-4-isostearate/hexyl laurate, or a mixture thereof, and highly preferred a mixture of cetyl dimethicone copolyol and lauryl dimethicone copolyol.
- the ratio of the low HLB emulsifier to the copolyol is preferably from about 1:1.5 to about 2.5:1.
- the cold-mix water-in-oil emulsion may further comprising from 0% to about 10% by weight an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof, a lightening agent, or a tanning agent (e.g. dihydroxy acetone).
- a tanning agent e.g. dihydroxy acetone
- the present invention encompasses a cold-mix method for preparing a cold mix water-in-oil emulsion comprising:
- R is substantially linear nor-oleyl, with water
- the method for preparing a cold mix water-in-oil emulsion may further comprise homogenizing the water-in-oil emulsion.
- the method for preparing a cold mix water-in-oil emulsion may further comprise adding to the water-in-oil emulsion an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof, a lightening agent, or a tanning agent (e.g. dihydroxy acetone).
- the preferred method embodiments, more preferred embodiments and most preferred embodiments include those preferred components, ingredients, and ratios described herein.
- the present invention encompasses a cold-mix water-in-oil sunscreen emulsion comprising:
- R is substantially linear nor-oleyl
- the emulsification system and the co-emulsifier substantially permanently maintain the water and emollient as a sunscreen emulsion, the sunscreen emulsion capable of being substantially completely emulsified and stable at about 25° C.
- the preferred cold-mix water-in-oil sunscreen emulsion embodiments include those preferred components, ingredients, and ratios described herein.
- Preferred sunscreens are titanium dioxide, zinc oxide, octyl methoxy-cinnamate, octyl salicylate avobenzone, benzophenone-4, or a mixture thereof.
- the cold-mix water-in-oil sunscreen emulsion may also further comprising an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof, a lightening agent, or a tanning agent (e.g. dihydroxy acetone).
- a tanning agent e.g. dihydroxy acetone
- the present invention encompasses a cold-mix method for preparing a cold mix water-in-oil sunscreen emulsion comprising:
- R is substantially linear nor-oleyl, with water
- the method for preparing a cold mix water-in-oil sunscreen emulsion may further comprise homogenizing the water-in-oil emulsion.
- the method for preparing a cold mix water-in-oil sunscreen emulsion may further comprise adding to the water-in-oil emulsion an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof, a lightening agent, or a tanning agent (e.g. dihydroxy acetone).
- the preferred method embodiments, more preferred embodiments and most preferred embodiments include those preferred components, ingredients, and ratios described herein.
- the present invention further encompasses a method for providing sun protection to human skin, comprising applying to said human skin a cold-mix water-in-oil sunscreen emulsion comprising:
- R is substantially linear nor-oleyl
- the emulsification system and the co-emulsifier substantially permanently maintain the water and emollient as a sunscreen emulsion, the sunscreen emulsion capable of being substantially completely emulsified and stable at about 25° C.
- the water-in-oil sunscreen emulsion additionally comprises an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof, a lightening agent, or a tanning agent (e.g. dihydroxy acetone) or a mixture thereof.
- a lightening agent e.g. dihydroxy acetone
- a tanning agent e.g. dihydroxy acetone
- Water-in-oil compositions of the invention generally comprise from 5-65% by weight, more preferably from 10-40% by weight, most preferably 15-25% by weight of an emollient, i.e., the oil phase.
- the oil phase may generally comprise any oily material that is immiscible with water.
- Preferred oil phase emollients emulsion include those mentioned herein.
- Silicone oils or fluids are used to improve the lubricity of the composition during application to the skin, as known to one of skill in the art. These silicone oils may optionally be included in the water-in-oil emulsions disclosed herein in minor amounts of about 0.5% to about 10% by weight. Preferably the viscosity of the optional silicone oil is from about 5 to about 12,500 centistokes at about 25° C. Examples of suitable optional silicone oils are dimethylpolysiloxane, diethylpolysiloxane, dimethylpolysiloxane-diphenylpolysiloxane, cyclomethicone, trimethylpolysiloxane, diphenylpolysiloxane, and mixtures thereof.
- the oil phase emollient may comprise further optional diluents such as, for example, low viscosity silicones (having a viscosity of between 0.1 to 1,000 mPa.s, more preferably 0.5 to 500 mPa.s, most preferably 0.65-100, liquid paraffins or methicones and other solvents such as C 10 to C 12 isoparaffins, including for example Isopar L (manufactured Esso), polyisobutene such as polysynlane (manufactured by Nippon Oils and Fats), squalane such as Squalene (manufactured by J. G.
- low viscosity silicones having a viscosity of between 0.1 to 1,000 mPa.s, more preferably 0.5 to 500 mPa.s, most preferably 0.65-100
- liquid paraffins or methicones and other solvents such as C 10 to C 12 isoparaffins, including for example Isopar
- branched chain hydrocarbons e.g., Permethyl 99A (manufactured by Presperse), Permethyl 101A, branched chain light paraffin oils such as Lytol (manufactured by Witco) or WM1 (manufactured by BP), mineral oil such as Marchol 82 (manufactured by Esso) or Carnation Oil (manufactured by Witco), long chain alkyl alkanoic esters such as decyl oleate (e.g., Cetiol V manufactured by Henkel), isopropyl myristate (e.g., Estol 1514 manufactured by Unichema) and glyceryl tri(2-ethyl hexanoate) e.g., Myritol CTEG manufactured by Henkel).
- decyl oleate e.g., Cetiol V manufactured by Henkel
- isopropyl myristate e.g., Est
- the optional silicone oil will comprise a cyclomethicone or dimethicone.
- such optional silicones may be represented by the formula:
- R is a 1 to 3 carbon alkyl group
- n is a number from 3 to 10, preferably from 3 to 7, and the unsatisfied valences on the oxygen and silicon atoms at the ends of the chain may optionally be joined to one another to form a cyclic structure.
- Suitable optional volatile silicones are, for example, U.C.C.
- Dimethicone a dimethylpolysiloxane end blocked with trimethyl units, having a viscosity between 10 and 1000 centistokes is a particularly preferred optional silicone agent.
- other optional volatile silicones may also be utilized, alone or in combination with optional non-volatile silicones.
- compositions may also be prepared to contain various petroleum products and lubricants, graphite lubricants, polybutene, polyethylene, linseed oil, and crude oil, as well as other oils and other solid or semi-solid materials.
- oils that may be used in the emulsions also include solvents and hydrocarbons such as, for example, mineral spirits, kerosene, terpenes, and glycol ethers.
- the oils may also be materials suitable for personal care products, e.g., mineral oil, caprylic/capric triglyceride, isopropyl myristate, isopropyl palmitate, octyl palmitate, octyl isononoate alkyl, esters of fatty acids having at least about 8 carbon atoms, or liquid alkyl esters of long chain fatty acids.
- a particularly preferred copolyol of the instant invention is cetyl dimethicone copolyol, available from T. H. Goldschmidt as Abil® EM-90.
- the most preferred ratio of the low HLB emulsifier to copolyol is from about 1:1 to about 2:1. It is preferred that the low HLB emulsifier of the invention be used in combination with a co-emulsifier although the co-emulsifier is not a required component.
- Water-in-oil compositions of the invention comprise from 35-95% by weight, more preferably from 60-90% by weight, most preferably from 75-85% by weight of an aqueous phase.
- the aqueous phase typically contains the low HLB emulsifier and water.
- the aqueous phase may for example further comprise one or more optional liquid water-miscible materials.
- Suitable optional materials are for example propylene glycol, glycerol, sorbitol and polyglycerol.
- polyether materials such as for example polyethyleneglycol or polypropylene glycol, ethoxylated polyols, e.g. Atlas G2330 manufactured by ICI and Glucum E10 manufactured by Amerchol and block copolymers of ethylene oxide and propylene oxide e.g. Synperonic L13 or ICI.
- the aqueous phase comprises 0-75% by weight of the optionally liquid water-miscible materials, more preferably 20-65%, most preferably 30-45%, based on the weight of the aqueous phase.
- Salts are sometimes optionally used to adjust the viscosity of cationic emulsions. However, in a distinct aspect of this invention, it has been found that salt in higher concentrations tends to destabilize the formulations of the present invention. It is preferred that the formulation be prepared in the substantial absence of added salt.
- the term “added salt” is meant to exclude salts formed as a consequence of adjusting the pH of other components added to the formulation. In more preferred embodiments of this invention, the total salt concentration of the formulation will be no more than 0.5 molar and more preferably is within the range from about 0.1 to about 0.2 molar.
- the optional electrolyte material may be selected from water soluble salts such as alkali (earth) metal salts such as sulphates, halogenides, formates, borates, benzoates, and (C 1-4 )tetra-alkyl ammonium halides etc.
- water soluble acids such as citric acid, and phosphoric acid may also optionally be used in minor amounts as prescribed above.
- Water soluble bases such as sodium hydroxide may also optionally be used.
- Water-in-oil emulsions according to the invention may take a variety of physical forms, for example they may be sprayable liquids, liquids, gels, pastes, etc.
- emulsions of the invention are flowable having a viscosity of about 2000-4500 cps, with lotion preferred viscosities of about 3000 to 4000 at 25° C., measured in a Brookfield RVT viscometer, spindle #4, 20 rpm.
- emulsions of the instant invention may also be readily flowable, water-thin, “spray on lotions” with much lower viscosities of about 10-50 cps.
- Water-in-oil emulsions of the invention may also include minor amounts of other optional ingredients such as surfactants, antibacterial agents, antidandruff agents, pearlescers, dyes, preservatives, sunscreens, viscosity modifiers, proteins, polymers, buffering agents, herb extracts, oils etc. Generally, these materials are only present in minor amounts, i.e., less that 3% by weight.
- Sunscreens are cosmetic compositions which are applied topically to human skin to provide protection against the harmful ultraviolet rays of the sun (UV-A and UV-B radiation, generally in the range of 290-400 nm).
- Conventional sunscreens are prepared using cosmetically acceptable lotions, oils, creams, and emulsions (both oil-in-water and water-in-oil).
- a sun screen additive such as octyl dimethyl para-aminobenzoic acid can be employed in the inventive composition in amounts preferably from about 1% to 8% by weight of the total composition.
- zinc oxide, titanium dioxide, and like ingredients can also be provided in amounts from about 0.1% to 15.0%, preferably from 1.0% to 10.0% by weight of the composition.
- Preferred organic sunscreen agents include benzophenone-3 (oxybenzone), benzophenone-4, menthyl anthranilate, octocrylene, octyl methoxycinnamate, and mixtures thereof.
- Other sunscreen agents such as octyl salicylate, PABA and derivatives may be used.
- OMC octyl methoxycinnamate
- UV protection agents that may be included in the emulsions include para-aminobenzoic acid, amido carboxylates (functionalized metallo soaps) such as lauryl succinamate, and aluminum stearate (lactate) (see e.g., U.S. Pat. Nos. 4,675,422 and 4,724,174).
- fatty alcohols typically monohydric alcohols used in the formulations of the invention stabilize the emulsions and provide a cosmetically acceptable viscosity. Selection of the fatty alcohol is not critical although C10, C12, C14 fatty alcohols are preferred, with C12 being the most preferred.
- the fatty alcohol is preferably included in the formulations of this invention at a concentration of about 0.3% to about 10% by weight of the emulsion composition, more preferably from about 0.5% to about 5% by weight.
- Fatty ester emollients enhance the tactile properties of the composition.
- suitable fatty esters for use in the formulation of the invention include isopropyl myristate, isopropyl palmitate, isopropyl isostearate, isostearyl isostearate, diisopropyl sebacate, propylene glycol dipelargonate, 2-ethylhexyl isononoate, 2-ethylhexyl stearate, C12-C16 fatty alcohol lactate, isopropyl lanolate, 2-ethyl-hexyl salicylate, and mixtures thereof.
- the presently preferred fatty ester is isopropyl palmitate, octyl isononoate.
- the fatty ester when included is preferably included in the formulations of this invention at a concentration of about 0.25% to about 40% by weight of the emulsion composition, more preferably from about 1% to about 25% by weight.
- a humectant may be optionally present in the compositions of the invention.
- humectants can be entrapped in the interstices of the surface stratum corneum, where they act as a hygroscopic agent, thus increasing the amount of water held in this area. The water is given up by the humectant, as required, to contribute to the softening of the skin surface.
- humectants can be employed in addition to or substituted partially for, the water component of the inventive emulsions.
- humectants employed in the formulations of this invention are water-soluble and are substantially nonionizable.
- substantially nonionizable it is meant that no significant or detectable disassociation in water occurs.
- Suitable humectants for the formulations of this invention include glycerin, propylene glycol, sorbitol, polyethylene glycol, 1,2,6-hexanetriol, hydrogenated starch hydrolysate, inositol, mannitol, PEG-5 pentaerythritol ether, polyglyceryl sorbitol, xylitol, sucrose, and the like.
- a particularly preferred humectant is glycerin which, apart from its water binding properties, is postulated to also visually improve the surface of dry skin.
- the humectant when present is preferably included in the formulations of this invention at a concentration of about 0.2% to about 5% by weight of the emulsion composition.
- alpha hydroxy acids are selected from the group consisting of citric acid, glycolic acid, glucuronic acid, galacturonic acid, alpha hydroxybutyric acid, alpha hydroxyisobutyric acid, lactic acid, malic acid, mandelic acid, mucic acid, pyruvic acid, alpha phenylactic acid, alpha phenylpyruvic acid, saccharic acid, tartaric acid, and tartronic acid.
- Glycolic acid, lactic acid, tartaric acid, and malic acid are particularly preferred.
- Other preferred acids are hydroxy, dihydroxy, and keto analogs of amino acids. Examples include glyceric acid, beta phenyl lactic acid, beta phenyl pyruvic acid, alpha hydroxy isovaleric acid, alpha hydroxy isocaproic acid, 2,3-dihydroxybutanoic acid, and 2,6-dihydroxyhexanoic.
- hydroxymonocarboxylic acids include hydroxymonocarboxylic acids, hydroxydicarboxylic acids, hydroxytricarboxylic acids, and keto acids.
- the hydroxy polycarboxylic acids may be provided as the alpha or beta analogs and may be present as free acids, peroxides, lactones, amides, esters, or salts.
- acids included are 2-hydroxyglutaric acid, 3,4-dihydroxyglutamic acid, 2,5-dihydroxy-6-aminohexanoic acid, acetopyruvic acid, acetyl pyruvic acid, beta-floropyruvic acid, tartaric acid, citric acid, 2-hydroxybenzoic acid (salicylic acid), 2-hydroxy-2-methylbutyric acid, 2-hydroxy isobutyric acid, mandelic acid, and 2-hydroxy caproic acid.
- ingredients which also may be optionally included are emulsifying agents, thickeners, moisturizers, preservatives, coloring agents, fragrances, antioxidants, lightening agents, tanning agents, and other active ingredients.
- emulsifying agents thickeners, moisturizers, preservatives, coloring agents, fragrances, antioxidants, lightening agents, tanning agents, and other active ingredients.
- various essential oils such as menthol and the like, can be employed in minor amounts from 0.1% to 2% by weight of the composition.
- the formulation may also contain other conventional additives employed in cosmetic emulsions.
- Such optional additives include aesthetic enhancers, natural extracts, fragrance oils, dyes, preservatives.
- Preferred aesthetic enhancers are polyquaternium 31 and aluminum starch octenylsuccinate.
- a skin care product is an oil-in-water emulsion for topical application which comprises from about 1% to about 8 weight %, most preferably from about 2% to 5% of a particular cationic emulsifier (i.e.
- a low HLB emulsifier optionally, from about 0.2% to about 15 weight %, preferably from 1% to 7% of a water-soluble humectant, and, optionally, a pharmaceutically acceptable, weakly acidic material in an amount sufficient to adjust the pH of the finished emulsion to a value in the range of about 2.0 to about 4.5, preferably 3.0 to 4.0, when the emulsion is diluted with purified water to 10 times its weight.
- these oil-in-water emulsions will include hydrogenated castor oil and/or microcrystalline wax.
- Water-in-oil emulsions of the invention may be prepared by any suitable method for the preparation of water-in-oil emulsions well know to those skilled in the art.
- a preferred method involves the separate preparation of the oil phase (i.e. the emollient) and the aqueous phase by mixing at about 25° C., followed by gradually adding the aqueous phase to the oil phase under stirring at about 25° C.
- the input of mixing energy should be high and should be maintained for a time sufficient to form a water-in-oil emulsion having a smooth appearance (indicating the presence of relatively small micelles in the emulsion).
- the water employed in the formulations and method of this invention is purified water obtained, e.g., by distilling ordinary tap water, by purifying ordinary water through an ion exchange resin, or by other techniques apparent to those skilled in the art.
- compositions of the present invention are topically applied in a conventional manner.
- the compositions may be dispensed from a container and then gently applied to the skin.
- the compositions are rapidly absorbed and leave the skin with a soft and smooth appearance.
- Weight percent refers to weight percent, based on total weight of the cold-mix emulsion, unless otherwise specified.
- Water-in-oil emulsions were prepared by first preparing a water phase comprising the low HLB emulsifier of the following formula, subsequently preparing the oil phase and combining the two phases with agitation at around 25° C., as further illustrated below.
- a B Ingredients % by wt. % Functionality PHASE A 1. D.I. Water q.s. to q.s. to Diluent 100.0 100.0 2. STEPANQUAT ® ML 1 2.0 2.0 Conditioning agent, emulsifier 3. KESSCO ® PEG 600 ML 2 0.5 0.5 Emollient PHASE B 4. Abil EM-90 3 1.0 1.0 Co- emulsifier 5. Silicone DC 345 4 20.0 20.0 Emollient 6. TiO 2 Kobo MT-100T 5 8.0 8.0 Physical sunscreen agent PHASE C 7. ZnO Z-COTE 6 — 2.0 Physical/ inorganic sunscreen agent 8.
- NEOBEE ® M-5 COSMETIC 7 5.0 Emollient, solvent PHASE D 9. Preservative, color, fragrance q.s. q.s. Additive Properties: Appearance Lotion Lotion SPF 25.0 Not tested 1 Quaternary Ammonium Compound (Stepan) 2 Polyethylene Glycol 600 Monolaurate (Stepan) 3 Cetyl dimethicone copolyol (Goldschmidt) 4 Cyclomethicone (Dow Corning) 5 Titanium Dioxide (Kobo). 6 Zinc Oxide BASF. 7 Caprylic/Capric Triglyceride (Stepan)
- phase A by combing items #1,2 and 3 at 25 C. with agitation.
- phase B by combining items #4, 5 and 6 at 25 C. with agitation.
- phase C by combining items #7 and 8 (for Formulation B) at 25 C. with agitation. Add phase C to the intermediate batch at 25 C. with agitation. Mix well for 15-20 minutes to form a main batch
- phase D to the main batch at 25 C. with agitation.
- Appearance Opaque lotion 1 Quaternary Ammonium Compound (Stepan) 2 Polyethylene Glycol 600 Monolaurate (Stepan) 3 Octyl Isonononoate (Stepan) 4 Cetyl dimethicone copolyol (Goldschmidt). 5 Cyclomethicone (Dow Corning).
- phase A by combining items #1,2 and 3 at 25 C. with agitation.
- phase B by combining items #4, 5 and 6 at 25 C. with agitation.
- phase D to the intermediate batch at 25 C. with agitation.
- phase A by combining items #1, 2 and 3 at 25 C. with agitation.
- phase B by combining items #4, 5, 6 and 7 at 25 C. with agitation.
- phase A by combining items #1, 2 and 3 at 25 C. with agitation.
- phase B by combining items #4 and 5 at 25 C. with agitation.
- phase C by combining items #6 and 7 at 25 C. with agitation. Add phase C to the intermediate batch at 25 C. with agitation. Mix well for 15-20 minutes to form a main batch.
- phase D to the main batch at 25 C. with agitation.
- phase A by combining items #1, 2 and 3 at 25 C. with agitation.
- phase B by combining items #4, 5, 6 and 7 at 25 C. with agitation.
- phase D to the intermediate batch at 25 C. with agitation.
- Appearance NOT Sprayable thick emulsion pH SPF 1 Quaternary Ammonium Compound (Stepan) 2 Polyethylene Glycol 600 Monolaurate (Stepan) 3 Cetyl dimethicone copolyol (Goldschmidt). 4 Cyclomethicone (Dow Corning) 5 Octyl Methoxycinnamate (ISP Van Dyk Inc.) 6 Octyl Salicylate (ISP Van Dyk Inc.)
- phase A by combining items #1, 2 and 3 at 25 C. with agitation.
- phase B by combining items #4, 5, 6 and 7 at 25 C. with agitation.
- phase D to the intermediate batch at 25 C. with agitation.
- phase A by combining items #1, 2 and 3 at 25 C. with agitation.
- phase B by combining items #4, 5, 6 and 7 at 25 C. with agitation.
- phase D to the intermediate batch at 25 C. with agitation.
- phase A by combining items #1, 2 and 3 at 25 C. with agitation.
- phase B by combining items #4, 5, 6 and 7 at 25 C. with agitation.
- phase D to the intermediate batch at 25C. with agitation.
- phase A by combining items #1, 2 and 3 at 25C. with agitation.
- phase B by combining items #4, 5, 6 and 7 at 25C. with agitation.
- phase D to the intermediate batch at 25C. with agitation.
- phase A by combining items #1,2, 3 and 4 at 25C. with agitation.
- phase D to the intermediate batch at 30-35 F. with agitation to form a main batch.
- phase A by combining items #1, 2 and 3 at 25 C. with agitation.
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Abstract
The present invention relates to stable cold-mix water-in-oil emulsions and methods for preparing such emulsions. The cold-mix water-in-oil emulsions comprise oil (i.e., an emollient), water and an emulsification system comprising a quaternary ammonium-based low HLB emulsifier and optional co-emulsifiers. The emulsions are useful in preparing finished cosmetic compositions in the form of lotions, gels, or sprays, which provide improved moisturization, skin feel, skin care, and/or appearance benefits and/or reduced greasiness, with excellent rub-in and absorption characteristics. Also disclosed are cold-mix water-in-oil sunscreen emulsions and methods for preparing such sunscreen emulsions. The emulsions of the instant invention are generally capable of being substantially completely emulsified and stable at about 25° C.
Description
This application claims the benefit of U.S. Provisional Application No. 60/146,597, filed Jul. 30, 1999.
Field of the Invention
The present invention relates to stable cold-mix water-in-oil emulsions and methods for preparing such emulsions. More specifically, the invention relates to cold-mix water-in-oil emulsions comprising oil (i.e., an emollient), water and an emulsification system comprising a quaternary ammonium-based low HLB emulsifier and optional co-emulsifiers. The present invention relates to cosmetic compositions which contain the inventive cold-mix oil and water emulsions. These cosmetic compositions are typically in the form of lotions, gels, or sprays, which provide improved moisturization, skin feel, skin care, and appearance benefits and reduced greasiness, together with excellent rub-in and absorption characteristics. The instant invention also relates to cold-mix water-in-oil sunscreen emulsions and methods for preparing such sunscreen emulsions. The emulsions of the instant invention generally display excellent extended duration stability characteristics at both normal and elevated temperatures.
Conventional cosmetic cream and lotion compositions, for example those in Sagarin, Cosmetics Science and Technology, 2nd Ed., Vol.1, Wiley Interscience (1972) and Encyclopedia of Chemical Technology, 3rd Ed., Vol. 7 are known to provide varying degrees of emolliency, barrier and water-retention (moisturizing) benefits. However, these conventional compositions are often lacking in desirable skin feel properties (i.e., they often feel very greasy when applied to the skin), as well as having poor rub-in, absorption and residue characteristics. Additional oil-in-water emulsion disclosures include for example those found in U.S. Pat. No. 5,759,558 (to Epstein, issued Jun. 2, 1998), U.S. Pat. No. 5,656,280 (to Helene Curtis, issued Aug. 12, 1997), U.S. Pat. No. 5,589,117 (to Helene Curtis, issued Dec. 31, 1996), U.S. Pat. No. 5,756,108 (to L'Oreal, issued May 26, 1998), U.S. Pat. No. 5,759,557 (to Epstein, issued Jun. 2, 1998), U.S. Pat. No. 5,543,136 (to NuSkin International, issued Aug. 6, 1996), U.S. Pat. No. 4,389,418 (to S. C. Johnson & Sons, issued Jun. 21, 1983), EP 0715842 A2 (Helene Curtis, filed Nov. 10, 1995), and WO 98/55086 (Stewart, filed Jun. 4, 1998).
While water-in-oil compositions are well known, they are difficult to prepare as they normally require heating to high temperatures (i.e., greater than 50° C.) and generally have not enjoyed commercial success and/or consumer popularity due to unacceptable greasiness. The disadvantages of preparing water-in-oil emulsions at higher temperatures include promotion of unacceptable water loss through evaporation, time-consummation, inefficient processing, and the added processing expense of heating the emulsion.
The foregoing description of the related art indicates that a variety of water-in-oil emulsions are known, along with a variety of processes to produce such emulsions, all of which have various end-use property limitations and/or undesirable processing limitations. A need exists for a superior processable water-in-oil emulsion which can be prepared at relatively low temperatures, i.e., at about 25° C. Additionally there is a need for such processable emulsions which do not impart a greasy feel to skin upon application, while at the same time such emulsion possess acceptable rub-in, absorption and residue characteristics.
Surprisingly, compositions of the instant invention can be prepared with little to no heat, i.e., they are prepared as a water-in-oil emulsion which is capable of being substantially completely emulsified and stable at about 25° C. In additional to highly desirable low temperature preparation, these emulsions are stable, light and have a non-greasy feel when applied to the skin. The present invention provides skin-care cosmetic compositions which provide improved moisturization, absorption, skin feel, skin care and appearance characteristics and, which in particular, provide improved short and longer term moisturizing effectiveness, while at the same time reducing stickiness and avoiding a greasy feel on the skin. The compositions also display excellent stability characteristics at both normal and elevated temperatures.
It is therefore an object of the present invention to provide cold-mix water-in-oil emulsions comprising oil (i.e., an emollient), water and an emulsification system comprising a quaternary ammonium-based low HLB emulsifier and optional co-emulsifiers. Another object of the invention is to provide cold-mix water-in-oil sunscreen emulsions comprising oil (i.e., an emollient), water, an emulsification system comprising a quaternary ammonium-based low HLB emulsifier and optional co-emulsifiers, and a sun screen agent. Another objection of the invention relates to bulk and finished cosmetic compositions (lotions, gels, sprays) which contain the inventive cold-mix water-in-oil emulsions and cold-mix water-in-oil sunscreen emulsions. The invention further relates to cold-mix methods of preparing the cold-mix water-in-oil emulsions disclosed, including the cold-mix water-in-oil sunscreen emulsions described herein.
It is another object of the present invention to provide methods for moisturizing and/or providing sun protection to human skin, comprising applying to the skin the cold-mix water-in-oil emulsions and/or the cold-mix water-in-oil sunscreen emulsions described herein.
These and other objects and advantages are achieved by the invention description below.
It has been surprisingly discovered that highly stable water-in-oil emulsions can be prepared as a cold mix water-in-oil emulsions at about 25° C. The present invention also encompasses cold mix water-in-oil sunscreen emulsions.
Accordingly, the present invention encompasses a cold-mix water-in-oil emulsion comprising:
(a) from about 10% to about 50% by weight of an emollient;
(b) from about 0.5% to about 30% by weight of an emulsification system comprising a low HLB emulsifier of the formula:
where R is substantially linear nor-oleyl;
(c) from about 0% to about 35% of a co-emulsifier; and
(d) water;
the emulsification system and co-emulsifier substantially permanently maintaining the water and emollient as an emulsion, the emulsion capable of being substantially completely emulsified and stable at about 25° C.
The present invention encompasses a cold-mix water-in-oil sunscreen emulsion comprising:
(a) from about 10% to about 30% by weight of an emollient; and
(b) from about 0.5% to about 30% by weight of an emulsification system comprising a low HLB emulsifier of the formula:
where R is substantially linear nor-oleyl;
(c) from about 0% to about 35% a co-emulsifier;
(d) a sunscreen agent; and
(e) water;
wherein the emulsification system and the co-emulsifier substantially permanently maintain the water and emollient as a sunscreen emulsion, the sunscreen emulsion capable of being substantially completely emulsified and stable at about 25° C.
The invention also includes methods for making and using such emulsions. The emulsions described herein are primarily useful in finished sun screening formulations for application to human skin and in finished moisturizing creams, lotions, gels, and sprays for application to human skin. The inventive emulsions may be topically applied to human skin to moisturize the skin and/or may also be applied to human skin before prolonged exposure to light radiation to prevent the erythema normally observed after such exposure, i.e. the prevention of sun burn.
The present invention encompasses novel cold-mix water-in-oil emulsions utilizing quaternary ammonium-based low HLB emulsifiers. The emulsions are readily prepared at low temperatures, i.e. at about 25° C. Further, the emulsification system and the co-emulsifier substantially permanently maintain the water and emollient as a water-in-oil emulsion, where such emulsion is substantially completely emulsified and stable at about 25° C.; by this it is meant that the water-in-oil emulsion and/or water-in-oil sunscreen emulsion remains substantially completely emulsified and does not phase separate in two or more layers (e.g., a water layer and an oil layer) at 25° C. for a minimum of 14 days.
The emulsions of the instant invention preferably contain sufficient amounts of ingredients that will produce an emulsion having a smooth, continuous appearance when emulsified. The term “low HLB emulsifier” as used herein means an emulsifier with an HLB below 12, and preferred HLB below 10. The term “HLB” as used herein means Hydrophilic-Lipophilic Balance. HLB is a reflection of the balance between the lipophilic and hydrophilic moieties of a molecule (surfactant or emulsifier), such as the low HLB emulsifiers described herein. This balance between the lipophilic and hydrophilic moieties of a molecule provides an HLB number that indicates the surfactant's or emulsifiers performance as an emulsifier. A lower HLB value indicates a more lipophilic surfactant, which is accordingly more oil-soluble. HLB values may be calculated by a variety of know methods to those skilled in the art. (See for example: Rosen, Surfactants and Interfacial Phenomena, 2nd ed., Wiley Interscience, 1989.)
As previously mentioned, the present invention encompasses a cold-mix water-in-oil emulsion comprising:
(a) from about 10% to about 50% by weight of an emollient;
(b) from about 0.5% to about 30% by weight of an emulsification system comprising a low HLB emulsifier of the formula:
where R is substantially linear nor-oleyl;
(c) from about 0% to about 35% of a co-emulsifier; and
(d) water;
the emulsification system and co-emulsifier substantially permanently maintaining the water and emollient as an emulsion, the emulsion capable of being substantially completely emulsified and stable at about 25° C. More preferably the cold-mix water-in-oil emulsion comprises from about 10% to about 30% by weight of the emollient, and most preferably from about 15% to about 25% by weight of the emollient. In a somewhat preferred embodiment, the cold-mix water-in-oil emulsion will comprise from about 0.5% to about 15% by weight of the low HLB emulsifier, more preferably from about 0.5% to about 8% by weight of the low HLB emulsifier, and most preferably from about 1% to about 3% by weight of the low HLB emulsifier.
Useful emollients are described in detail below. Preferred emollients are dimethicone, cyclomethicone, triglycerides, alcohol esters, ethoxylated esters, hydrocarbons, natural oils or a mixture thereof. Of these preferred emollients, the preferred hydrocarbon are mineral oil, mineral spirits, isohexadecane, or a mixture thereof. The most preferred emollients are triglycerides, alcohol esters, ethoxylated esters, glycol ethers, natural oils or a mixture thereof. Of these, preferred natural oils include safflower oil, jojoba oil, sunflower oil, or a mixture thereof.
The cold-mix water-in-oil emulsion of the invention can additionally comprise a water-soluble nonionic surfactant. Preferred water-soluble nonionic surfactants are selected from the group consisting of polyethylene glycol laurate, polyethylene glycol dilaurate, or a mixture thereof.
In another preferred embodiment, the cold-mix water-in-oil emulsion comprises from about 0.2% to about 22.5% by weight of the co-emulsifier, more preferably from about 0.2% to about 12.0% by weight of the co-emulsifier and most preferably from about 0.4% to about 4.5% by weight of the co-emulsifier.
A preferred co-emulsifier is a dimethicone copolyol, selected from the group consisting of a cyclomethicone-dimethicone copolyol mixture, lauryl dimethicone copolyol, cetyl dimethicone copolyol, cetyl dimethicone copolyol/polyglyceryl-4-isostearate/hexyl laurate, or a mixture thereof, and highly preferred a mixture of cetyl dimethicone copolyol and lauryl dimethicone copolyol. The ratio of the low HLB emulsifier to the copolyol is preferably from about 1:1.5 to about 2.5:1.
The cold-mix water-in-oil emulsion may further comprising from 0% to about 10% by weight an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof, a lightening agent, or a tanning agent (e.g. dihydroxy acetone).
The present invention encompasses a cold-mix method for preparing a cold mix water-in-oil emulsion comprising:
(a) preparing an oil phase by combining an emollient and a co-emulsifier at about 25° C.;
where R is substantially linear nor-oleyl, with water;
(c) combining the aqueous phase and the oil phase with agitation to produce an intermediate mixture;
(d) emulsifying the intermediate mixture to produce a water and oil emulsion which is substantially completely emulsified and stable at about 25° C.
The method for preparing a cold mix water-in-oil emulsion may further comprise homogenizing the water-in-oil emulsion. The method for preparing a cold mix water-in-oil emulsion may further comprise adding to the water-in-oil emulsion an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof, a lightening agent, or a tanning agent (e.g. dihydroxy acetone). The preferred method embodiments, more preferred embodiments and most preferred embodiments include those preferred components, ingredients, and ratios described herein.
The present invention encompasses a cold-mix water-in-oil sunscreen emulsion comprising:
(a) from about 10% to about 30% by weight of an emollient; and
(b) from about 0.5% to about 30% by weight of an emulsification system comprising a low HLB emulsifier of the formula:
where R is substantially linear nor-oleyl;
(c) from about 0% to about 35% a co-emulsifier;
(d) from about 0.1% to about 15% by weight of a sunscreen agent; and
(e) water;
wherein the emulsification system and the co-emulsifier substantially permanently maintain the water and emollient as a sunscreen emulsion, the sunscreen emulsion capable of being substantially completely emulsified and stable at about 25° C.
The preferred cold-mix water-in-oil sunscreen emulsion embodiments, more preferred embodiments and most preferred embodiments include those preferred components, ingredients, and ratios described herein. Preferred sunscreens are titanium dioxide, zinc oxide, octyl methoxy-cinnamate, octyl salicylate avobenzone, benzophenone-4, or a mixture thereof.
The cold-mix water-in-oil sunscreen emulsion may also further comprising an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof, a lightening agent, or a tanning agent (e.g. dihydroxy acetone).
The present invention encompasses a cold-mix method for preparing a cold mix water-in-oil sunscreen emulsion comprising:
(a) preparing an oil phase by combining an emollient and a co-emulsifier at about 25° C.;
where R is substantially linear nor-oleyl, with water;
(c) combining the aqueous phase and the oil phase with agitation to produce an intermediate mixture;
(d) emulsifying the intermediate mixture to produce a water-in-oil emulsion which is substantially completely emulsified and stable at about 25° C.; and
(e) combining a sunscreen agent with the water-in-oil emulsion to produce a water-in-oil sunscreen emulsion which is substantially completely emulsified and stable at about 25° C.
The method for preparing a cold mix water-in-oil sunscreen emulsion may further comprise homogenizing the water-in-oil emulsion. The method for preparing a cold mix water-in-oil sunscreen emulsion may further comprise adding to the water-in-oil emulsion an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof, a lightening agent, or a tanning agent (e.g. dihydroxy acetone). The preferred method embodiments, more preferred embodiments and most preferred embodiments include those preferred components, ingredients, and ratios described herein.
The present invention further encompasses a method for providing sun protection to human skin, comprising applying to said human skin a cold-mix water-in-oil sunscreen emulsion comprising:
(a) from about 10% to about 30% by weight of an emollient;
(b) from about 0.5% to about 30% by weight of an emulsification system comprising a low HLB emulsifier of the formula:
where R is substantially linear nor-oleyl;
(c) from about 0% to about 35% a co-emulsifier;
(d) from about 0.1% to about 15% by weight of a sunscreen agent; and
(e) water;
wherein the emulsification system and the co-emulsifier substantially permanently maintain the water and emollient as a sunscreen emulsion, the sunscreen emulsion capable of being substantially completely emulsified and stable at about 25° C.
In another embodiment of the method for providing sun protection to human skin, the water-in-oil sunscreen emulsion additionally comprises an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof, a lightening agent, or a tanning agent (e.g. dihydroxy acetone) or a mixture thereof. The preferred methods for providing sun protection to human skin embodiments, more preferred embodiments and most preferred embodiments include those preferred components, ingredients, and ratios described herein.
Emollients
Water-in-oil compositions of the invention generally comprise from 5-65% by weight, more preferably from 10-40% by weight, most preferably 15-25% by weight of an emollient, i.e., the oil phase. The oil phase may generally comprise any oily material that is immiscible with water. Preferred oil phase emollients emulsion include those mentioned herein.
Optional Silicones
Silicone oils or fluids are used to improve the lubricity of the composition during application to the skin, as known to one of skill in the art. These silicone oils may optionally be included in the water-in-oil emulsions disclosed herein in minor amounts of about 0.5% to about 10% by weight. Preferably the viscosity of the optional silicone oil is from about 5 to about 12,500 centistokes at about 25° C. Examples of suitable optional silicone oils are dimethylpolysiloxane, diethylpolysiloxane, dimethylpolysiloxane-diphenylpolysiloxane, cyclomethicone, trimethylpolysiloxane, diphenylpolysiloxane, and mixtures thereof.
Alternatively the oil phase emollient may comprise further optional diluents such as, for example, low viscosity silicones (having a viscosity of between 0.1 to 1,000 mPa.s, more preferably 0.5 to 500 mPa.s, most preferably 0.65-100, liquid paraffins or methicones and other solvents such as C10 to C12 isoparaffins, including for example Isopar L (manufactured Esso), polyisobutene such as polysynlane (manufactured by Nippon Oils and Fats), squalane such as Squalene (manufactured by J. G. Marthens), branched chain hydrocarbons e.g., Permethyl 99A (manufactured by Presperse), Permethyl 101A, branched chain light paraffin oils such as Lytol (manufactured by Witco) or WM1 (manufactured by BP), mineral oil such as Marchol 82 (manufactured by Esso) or Carnation Oil (manufactured by Witco), long chain alkyl alkanoic esters such as decyl oleate (e.g., Cetiol V manufactured by Henkel), isopropyl myristate (e.g., Estol 1514 manufactured by Unichema) and glyceryl tri(2-ethyl hexanoate) e.g., Myritol CTEG manufactured by Henkel).
In somewhat more preferred embodiments, the optional silicone oil will comprise a cyclomethicone or dimethicone. Generally such optional silicones may be represented by the formula:
wherein R is a 1 to 3 carbon alkyl group, n is a number from 3 to 10, preferably from 3 to 7, and the unsatisfied valences on the oxygen and silicon atoms at the ends of the chain may optionally be joined to one another to form a cyclic structure. Suitable optional volatile silicones are, for example, U.C.C. Y-7207, sold by Union Carbide Corporation in which each R (based on the above structure) is methyl and which typically comprises by weight 99.4% tetramer, 0.6% trimer and traces of the pentamer and hexamer; SWS-03314, sold by SWS Silicones, a Division of Stauffer Chemical Company, in which R based on the above structure) is methyl and which is substantially all pentamer; and Dow Corning 345 fluid, sold by Dow Corning, Inc., in which R (based on the above structure) is methyl and which typically comprises by weight about 88% pentamer, about 11.8% tetramer and traces of trimer and hexamer.
Dimethicone, a dimethylpolysiloxane end blocked with trimethyl units, having a viscosity between 10 and 1000 centistokes is a particularly preferred optional silicone agent. In addition, other optional volatile silicones may also be utilized, alone or in combination with optional non-volatile silicones.
It is also possible to employ optional vegetable oils, animal oils, (For oil-in-water emulsions, compositions may also be prepared to contain various petroleum products and lubricants, graphite lubricants, polybutene, polyethylene, linseed oil, and crude oil, as well as other oils and other solid or semi-solid materials.
The oils that may be used in the emulsions also include solvents and hydrocarbons such as, for example, mineral spirits, kerosene, terpenes, and glycol ethers. The oils may also be materials suitable for personal care products, e.g., mineral oil, caprylic/capric triglyceride, isopropyl myristate, isopropyl palmitate, octyl palmitate, octyl isonononoate alkyl, esters of fatty acids having at least about 8 carbon atoms, or liquid alkyl esters of long chain fatty acids.
A particularly preferred copolyol of the instant invention is cetyl dimethicone copolyol, available from T. H. Goldschmidt as Abil® EM-90. The most preferred ratio of the low HLB emulsifier to copolyol is from about 1:1 to about 2:1. It is preferred that the low HLB emulsifier of the invention be used in combination with a co-emulsifier although the co-emulsifier is not a required component.
The Aqueous Phase
Water-in-oil compositions of the invention comprise from 35-95% by weight, more preferably from 60-90% by weight, most preferably from 75-85% by weight of an aqueous phase. The aqueous phase typically contains the low HLB emulsifier and water. In addition, the aqueous phase may for example further comprise one or more optional liquid water-miscible materials. Suitable optional materials are for example propylene glycol, glycerol, sorbitol and polyglycerol. Also suitable are polyether materials such as for example polyethyleneglycol or polypropylene glycol, ethoxylated polyols, e.g. Atlas G2330 manufactured by ICI and Glucum E10 manufactured by Amerchol and block copolymers of ethylene oxide and propylene oxide e.g. Synperonic L13 or ICI.
The aqueous phase comprises 0-75% by weight of the optionally liquid water-miscible materials, more preferably 20-65%, most preferably 30-45%, based on the weight of the aqueous phase.
Salts
Salts are sometimes optionally used to adjust the viscosity of cationic emulsions. However, in a distinct aspect of this invention, it has been found that salt in higher concentrations tends to destabilize the formulations of the present invention. It is preferred that the formulation be prepared in the substantial absence of added salt. The term “added salt” is meant to exclude salts formed as a consequence of adjusting the pH of other components added to the formulation. In more preferred embodiments of this invention, the total salt concentration of the formulation will be no more than 0.5 molar and more preferably is within the range from about 0.1 to about 0.2 molar.
The optional electrolyte material may be selected from water soluble salts such as alkali (earth) metal salts such as sulphates, halogenides, formates, borates, benzoates, and (C1-4)tetra-alkyl ammonium halides etc. Water soluble acids such as citric acid, and phosphoric acid may also optionally be used in minor amounts as prescribed above. Water soluble bases such as sodium hydroxide may also optionally be used.
Physical Form
Water-in-oil emulsions according to the invention may take a variety of physical forms, for example they may be sprayable liquids, liquids, gels, pastes, etc. Preferably emulsions of the invention are flowable having a viscosity of about 2000-4500 cps, with lotion preferred viscosities of about 3000 to 4000 at 25° C., measured in a Brookfield RVT viscometer, spindle #4, 20 rpm. In another embodiment, emulsions of the instant invention may also be readily flowable, water-thin, “spray on lotions” with much lower viscosities of about 10-50 cps.
Other Ingredients
Water-in-oil emulsions of the invention may also include minor amounts of other optional ingredients such as surfactants, antibacterial agents, antidandruff agents, pearlescers, dyes, preservatives, sunscreens, viscosity modifiers, proteins, polymers, buffering agents, herb extracts, oils etc. Generally, these materials are only present in minor amounts, i.e., less that 3% by weight.
Sunscreens
Other ingredients can be employed in the inventive emulsions to provide a specifically tailored cosmetic composition. Sunscreens are cosmetic compositions which are applied topically to human skin to provide protection against the harmful ultraviolet rays of the sun (UV-A and UV-B radiation, generally in the range of 290-400 nm). Conventional sunscreens are prepared using cosmetically acceptable lotions, oils, creams, and emulsions (both oil-in-water and water-in-oil). For example, a sun screen additive, such as octyl dimethyl para-aminobenzoic acid can be employed in the inventive composition in amounts preferably from about 1% to 8% by weight of the total composition. To provide a skin protectant composition, zinc oxide, titanium dioxide, and like ingredients can also be provided in amounts from about 0.1% to 15.0%, preferably from 1.0% to 10.0% by weight of the composition.
Preferred organic sunscreen agents include benzophenone-3 (oxybenzone), benzophenone-4, menthyl anthranilate, octocrylene, octyl methoxycinnamate, and mixtures thereof. Other sunscreen agents such as octyl salicylate, PABA and derivatives may be used. When the emulsion contains octyl methoxycinnamate (“OMC”), an amount up to 10.0%, by weight of the total emulsion may be used.
Other ultraviolet protection agents that may be included in the emulsions include para-aminobenzoic acid, amido carboxylates (functionalized metallo soaps) such as lauryl succinamate, and aluminum stearate (lactate) (see e.g., U.S. Pat. Nos. 4,675,422 and 4,724,174).
Fatty Alcohols
Without being bound by any particular theory, fatty alcohols (typically monohydric alcohols) used in the formulations of the invention stabilize the emulsions and provide a cosmetically acceptable viscosity. Selection of the fatty alcohol is not critical although C10, C12, C14 fatty alcohols are preferred, with C12 being the most preferred. When used, the fatty alcohol is preferably included in the formulations of this invention at a concentration of about 0.3% to about 10% by weight of the emulsion composition, more preferably from about 0.5% to about 5% by weight.
Fatty Esters
Fatty ester emollients enhance the tactile properties of the composition. Examples of suitable fatty esters for use in the formulation of the invention include isopropyl myristate, isopropyl palmitate, isopropyl isostearate, isostearyl isostearate, diisopropyl sebacate, propylene glycol dipelargonate, 2-ethylhexyl isononoate, 2-ethylhexyl stearate, C12-C16 fatty alcohol lactate, isopropyl lanolate, 2-ethyl-hexyl salicylate, and mixtures thereof. The presently preferred fatty ester is isopropyl palmitate, octyl isonononoate. The fatty ester when included is preferably included in the formulations of this invention at a concentration of about 0.25% to about 40% by weight of the emulsion composition, more preferably from about 1% to about 25% by weight.
Humectants
If desired, a humectant may be optionally present in the compositions of the invention. Without being bound by any particular theory, it has been postulated that humectants can be entrapped in the interstices of the surface stratum corneum, where they act as a hygroscopic agent, thus increasing the amount of water held in this area. The water is given up by the humectant, as required, to contribute to the softening of the skin surface. Such humectants can be employed in addition to or substituted partially for, the water component of the inventive emulsions.
The humectants employed in the formulations of this invention are water-soluble and are substantially nonionizable. By “substantially nonionizable” it is meant that no significant or detectable disassociation in water occurs. Suitable humectants for the formulations of this invention include glycerin, propylene glycol, sorbitol, polyethylene glycol, 1,2,6-hexanetriol, hydrogenated starch hydrolysate, inositol, mannitol, PEG-5 pentaerythritol ether, polyglyceryl sorbitol, xylitol, sucrose, and the like. A particularly preferred humectant is glycerin which, apart from its water binding properties, is postulated to also visually improve the surface of dry skin. The humectant when present is preferably included in the formulations of this invention at a concentration of about 0.2% to about 5% by weight of the emulsion composition.
Acidic Materials and Alpha-/Beta Hydroxy Acids
The use of weakly acidic components is optional in the present invention and is not believed critical, although alpha hydroxy acids are presently preferred if such components are employed in the emulsions. Preferred alpha-hydroxy acids are selected from the group consisting of citric acid, glycolic acid, glucuronic acid, galacturonic acid, alpha hydroxybutyric acid, alpha hydroxyisobutyric acid, lactic acid, malic acid, mandelic acid, mucic acid, pyruvic acid, alpha phenylactic acid, alpha phenylpyruvic acid, saccharic acid, tartaric acid, and tartronic acid. Glycolic acid, lactic acid, tartaric acid, and malic acid are particularly preferred.
Other preferred acids are hydroxy, dihydroxy, and keto analogs of amino acids. Examples include glyceric acid, beta phenyl lactic acid, beta phenyl pyruvic acid, alpha hydroxy isovaleric acid, alpha hydroxy isocaproic acid, 2,3-dihydroxybutanoic acid, and 2,6-dihydroxyhexanoic.
Other useful acids include hydroxymonocarboxylic acids, hydroxydicarboxylic acids, hydroxytricarboxylic acids, and keto acids. The hydroxy polycarboxylic acids may be provided as the alpha or beta analogs and may be present as free acids, peroxides, lactones, amides, esters, or salts. Illustrative of the variety of acids included are 2-hydroxyglutaric acid, 3,4-dihydroxyglutamic acid, 2,5-dihydroxy-6-aminohexanoic acid, acetopyruvic acid, acetyl pyruvic acid, beta-floropyruvic acid, tartaric acid, citric acid, 2-hydroxybenzoic acid (salicylic acid), 2-hydroxy-2-methylbutyric acid, 2-hydroxy isobutyric acid, mandelic acid, and 2-hydroxy caproic acid.
Other Optional Ingredients
Other ingredients which also may be optionally included are emulsifying agents, thickeners, moisturizers, preservatives, coloring agents, fragrances, antioxidants, lightening agents, tanning agents, and other active ingredients. As a medicament, various essential oils, such as menthol and the like, can be employed in minor amounts from 0.1% to 2% by weight of the composition.
The formulation may also contain other conventional additives employed in cosmetic emulsions. Such optional additives include aesthetic enhancers, natural extracts, fragrance oils, dyes, preservatives. Preferred aesthetic enhancers are polyquaternium 31 and aluminum starch octenylsuccinate.
Oil-in-Water Emulsions
In another embodiment of the instant invention, other applications for the low HLB emulsifier of this invention are oil-in-water emulsions. A skin care product is an oil-in-water emulsion for topical application which comprises from about 1% to about 8 weight %, most preferably from about 2% to 5% of a particular cationic emulsifier (i.e. a low HLB emulsifier), optionally, from about 0.2% to about 15 weight %, preferably from 1% to 7% of a water-soluble humectant, and, optionally, a pharmaceutically acceptable, weakly acidic material in an amount sufficient to adjust the pH of the finished emulsion to a value in the range of about 2.0 to about 4.5, preferably 3.0 to 4.0, when the emulsion is diluted with purified water to 10 times its weight. Optionally, these oil-in-water emulsions will include hydrogenated castor oil and/or microcrystalline wax.
Water-in-oil emulsions of the invention may be prepared by any suitable method for the preparation of water-in-oil emulsions well know to those skilled in the art. A preferred method involves the separate preparation of the oil phase (i.e. the emollient) and the aqueous phase by mixing at about 25° C., followed by gradually adding the aqueous phase to the oil phase under stirring at about 25° C.
The input of mixing energy should be high and should be maintained for a time sufficient to form a water-in-oil emulsion having a smooth appearance (indicating the presence of relatively small micelles in the emulsion).
The water employed in the formulations and method of this invention is purified water obtained, e.g., by distilling ordinary tap water, by purifying ordinary water through an ion exchange resin, or by other techniques apparent to those skilled in the art.
Application
The skin care compositions of the present invention are topically applied in a conventional manner. In general, the compositions may be dispensed from a container and then gently applied to the skin. The compositions are rapidly absorbed and leave the skin with a soft and smooth appearance.
“Weight percent”, as used throughout this specification and in the claims, refers to weight percent, based on total weight of the cold-mix emulsion, unless otherwise specified.
All documents, e.g., patents and journal articles, cited above or below are hereby incorporated by reference in their entirety. In the following examples, all amounts are stated in percent by weight of active material unless indicated otherwise. One skilled in the art will recognize that modifications may be made in the present invention without deviating from the spirit or scope of the invention. The invention is illustrated further by the following examples which are not to be construed as limiting the invention or scope of the specific procedures or compositions described herein. All levels and ranges, temperatures, results etc., used herein are approximations unless otherwise specified.
Water-in-oil emulsions were prepared by first preparing a water phase comprising the low HLB emulsifier of the following formula, subsequently preparing the oil phase and combining the two phases with agitation at around 25° C., as further illustrated below.
| A | B | ||
| Ingredients | % by wt. | % | Functionality |
| PHASE A | |||
| 1. D.I. Water | q.s. to | q.s. to | Diluent |
| 100.0 | 100.0 | ||
| 2. STEPANQUAT ® ML1 | 2.0 | 2.0 | Conditioning |
| agent, | |||
| emulsifier | |||
| 3. KESSCO ® PEG 600 ML2 | 0.5 | 0.5 | Emollient |
| PHASE B | |||
| 4. Abil EM-903 | 1.0 | 1.0 | Co- |
| emulsifier | |||
| 5. Silicone DC 3454 | 20.0 | 20.0 | Emollient |
| 6. TiO2 Kobo MT-100T5 | 8.0 | 8.0 | Physical |
| sunscreen | |||
| agent | |||
| PHASE C | |||
| 7. ZnO Z-COTE6 | — | 2.0 | Physical/ |
| inorganic | |||
| sunscreen | |||
| agent | |||
| 8. NEOBEE ® M-5 COSMETIC7 | — | 5.0 | Emollient, |
| solvent | |||
| PHASE D | |||
| 9. Preservative, color, fragrance | q.s. | q.s. | Additive |
| Properties: | |||
| Appearance | Lotion | Lotion | |
| SPF | 25.0 | Not tested | |
| 1Quaternary Ammonium Compound (Stepan) | |||
| 2Polyethylene Glycol 600 Monolaurate (Stepan) | |||
| 3Cetyl dimethicone copolyol (Goldschmidt) | |||
| 4Cyclomethicone (Dow Corning) | |||
| 5Titanium Dioxide (Kobo). | |||
| 6Zinc Oxide BASF. | |||
| 7Caprylic/Capric Triglyceride (Stepan) | |||
Mixing Procedure
1. Prepare phase A by combing items #1,2 and 3 at 25 C. with agitation.
2. Prepare phase B by combining items #4, 5 and 6 at 25 C. with agitation.
3. Combine phase A and phase B while maintaining good agitation at about 25° C. to form an intermediate batch.
4. Prepare phase C by combining items #7 and 8 (for Formulation B) at 25 C. with agitation. Add phase C to the intermediate batch at 25 C. with agitation. Mix well for 15-20 minutes to form a main batch
5. Add phase D to the main batch at 25 C. with agitation.
6. Homogenize the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
| C | D | ||
| Ingredients | % by wt. | % | Functionality |
| PHASE A | |||
| 1. D.I. Water | q.s. to 100.0 | q.s. to | Diluent |
| 100.0 | |||
| 2. STEPANQUAT ® ML1 | 2.0 | 2.0 | Conditioning |
| agent, | |||
| emulsifier | |||
| 3. KESSCO ® PEG 600 ML2 | 0.5 | 0.5 | Emollient |
| PHASE B | |||
| 4. KESSCO ® OCTYL | 20.0 | — | Emollient |
| ISONONANOATE3 | |||
| 5. Abil EM-904 | 1.0 | 1.0 | Co- |
| emulsifier | |||
| 6. Silicone DC 3455 | — | 20.0 | Emollient |
| PHASE C | |||
| PHASE D | |||
| 7. Preservative, color, fragrance | q.s. | q.s. | Additive |
| Properties: | |||
| Appearance | Opaque | ||
| lotion | |||
| 1Quaternary Ammonium Compound (Stepan) | |||
| 2Polyethylene Glycol 600 Monolaurate (Stepan) | |||
| 3Octyl Isonononoate (Stepan) | |||
| 4Cetyl dimethicone copolyol (Goldschmidt). | |||
| 5Cyclomethicone (Dow Corning). | |||
Mixing Procedure
1. Prepare phase A by combining items #1,2 and 3 at 25 C. with agitation.
2. Prepare phase B by combining items #4, 5 and 6 at 25 C. with agitation.
3. Combine phase A and phase B while maintaining good agitation at about 25° C. to form an intermediate batch.
4. Add phase D to the intermediate batch at 25 C. with agitation.
5. Homogenize the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
| Ingredients | % by wt. | Functionality |
| PHASE A | ||
| 1. D.I. Water | q.s. to 100.0 | Diluent |
| 2. STEPANQUAT ® ML1 | 2.0 | Conditioning agent, |
| emulsifier | ||
| 3. KESSCO ® PEG 600 ML2 | 0.5 | Emollient |
| PHASE B | ||
| 4. Abil EM-903 | 1.0 | Co-Emulsifier |
| 5. Silicone DC 3454 | 20.0 | Emollient |
| 6. Lipocol L5 | 1.5 | Bodifying Agent |
| 7. GLYPURE (70% active) | 7.2 | Exfoliating Agent |
| PHASE C | ||
| PHASE D | ||
| 8. Preservative, color, fragrance | q.s. | Additive |
| Properties: | ||
| Appearance | Lotion-like | |
| pH | 3.0-3.5 | |
| SPF | ||
| 1Quaternary Ammonium Compound (Stepan) | ||
| 2PEG 600 Monolaurate (Stepan) | ||
| 3Goldschmidt (Cetyl dimethicone copolyol). | ||
| 4Cyclomethicone (Dow Corning) | ||
| 5Lauryl Alcohol (Lipo Chemicals Inc.) | ||
| 6Glycolic Acid (DuPont Chemicals) | ||
Mixing Procedure
1. Prepare phase A by combining items #1, 2 and 3 at 25 C. with agitation.
2. Prepare phase B by combining items #4, 5, 6 and 7 at 25 C. with agitation.
3. Combine phase A and phase B maintaining good agitation at about 25° C. to form an intermediate mixture.
4. Add phase D to the intermediate mixture at 25 C. with agitation.
5. Homogenize the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
| Ingredients | % by wt. | Functionality |
| PHASE A | ||
| 1. D.I. Water | q.s. to 100.0 | Diluent |
| 2. STEPANQUAT ® ML1 | 2.0 | Conditioning agent, |
| emulsifier | ||
| 3. KESSCO ® PEG 600 ML2 | 0.5 | Emollient |
| PHASE B | ||
| 4. Abil EM-903 | 1.0 | Co-Emulsifier |
| 5. Silicone DC 3454 | 20.0 | Emollient |
| PHASE C | ||
| 6. ZnO Z-COTE5 | 5.0 | Physical/inorganic |
| sunscreen agent | ||
| 7. NEOBEE ® M-5 COSMETIC6 | 5.0 | Emollient, solvent |
| PHASE D | ||
| 8. Preservative, color, fragrance | q.s. | Additive |
| Properties: | ||
| Appearance | ||
| pH | ||
| SPF | ||
| 1Quaternary Ammonium Compound (Stepan) | ||
| 2Polyethylene Glycol 600 Monolaurate (Stepan) | ||
| 3Cetyl dimethicone copolyol (Goldschmidt). | ||
| 4Cyclomethicone (Dow Corning) | ||
| 5Zinc Oxide (BASF) | ||
| 6Caprylic/Capric Triglyceride (Stepan). | ||
Mixing Procedure
1. Prepare phase A by combining items #1, 2 and 3 at 25 C. with agitation.
2. Prepare phase B by combining items #4 and 5 at 25 C. with agitation.
3. Combine phase A and phase B while maintaining good agitation at about 25° C. to form an intermediate batch.
4. Prepare phase C by combining items #6 and 7 at 25 C. with agitation. Add phase C to the intermediate batch at 25 C. with agitation. Mix well for 15-20 minutes to form a main batch.
5. Add phase D to the main batch at 25 C. with agitation.
6. Homogenize the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
| Ingredients | % by wt. | Functionality |
| PHASE A | ||
| 1. D.I. Water | q.s. to 100.0 | Diluent |
| 2. STEPANQUAT ® ML1 | 2.5 | Conditioning agent, |
| emulsifier | ||
| 3. KESSCO ® PEG 600 ML2 | 0.5 | Emollient |
| PHASE B | ||
| 4. Abil EM-903 | 1.5 | Co-Emulsifier |
| 5. Silicone DC 3454 | 10.0 | Emollient |
| 6. Parsol MCX5 | 7.5 | Organic Sunscreen |
| 7. Escalol 5876 | 5.0 | Organic Sunscreen |
| PHASE C | ||
| PHASE D | ||
| 8. Preservative, color, fragrance | q.s. | Additive |
| Properties: | ||
| Appearance | Sprayable, water-thin emulsion |
| pH | |
| SPF | |
| 1Quaternary Ammonium Compound (Stepan) | |
| 2Polyethylene Glycol 600 Monolaurate (Stepan) | |
| 3Cetyl dimethicone copolyol (Goldschmidt). | |
| 4Cyclomethicone (Dow Corning) | |
| 5Octyl Methoxycinnamate (Roche Chemicals) | |
| 6Octyl Salicylate (ISP Van Dyk Inc.) | |
Mixing Procedure
1. Prepare phase A by combining items #1, 2 and 3 at 25 C. with agitation.
2. Prepare phase B by combining items #4, 5, 6 and 7 at 25 C. with agitation.
3. Combine phase A and phase B while maintaining good agitation at about 25 C. to form an intermediate batch.
4. Add phase D to the intermediate batch at 25 C. with agitation.
5. Homogenize the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
| Ingredients | % by wt. | Functionality |
| PHASE A | ||
| 1. D.I. Water | q.s. to 100.0 | Diluent |
| 2. STEPANQUAT ® ML1 | 2.5 | Conditioning agent, |
| emulsifier | ||
| 3. KESSCO ® PEG 600 ML2 | 0.5 | Emollient |
| PHASE B | ||
| 4. Abil EM-903 | 1.5 | Co-Emulsifier |
| 5. Permethyl 101A4 | 10.0 | Emollient |
| 6. Escalol 5575 | 7.5 | Organic Sunscreen |
| 7. Escalol 5876 | 5.0 | Organic Sunscreen |
| PHASE C | ||
| PHASE D | ||
| 8. Preservative, color, fragrance | q.s. | Additive |
| Properties: | ||
| Appearance | NOT Sprayable, thick emulsion |
| pH | |
| SPF | |
| 1Quaternary Ammonium Compound (Stepan) | |
| 2Polyethylene Glycol 600 Monolaurate (Stepan) | |
| 3Cetyl dimethicone copolyol (Goldschmidt). | |
| 4Cyclomethicone (Dow Corning) | |
| 5Octyl Methoxycinnamate (ISP Van Dyk Inc.) | |
| 6Octyl Salicylate (ISP Van Dyk Inc.) | |
Mixing Procedure
1. Prepare phase A by combining items #1, 2 and 3 at 25 C. with agitation.
2. Prepare phase B by combining items #4, 5, 6 and 7 at 25 C. with agitation.
3. Combine phase A and phase B while maintaining good agitation at about 25 C. to form an intermediate batch.
4. Add phase D to the intermediate batch at 25 C. with agitation.
5. Homogenize the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
| Ingredients | % by wt. | Functionality |
| PHASE A | ||
| 1. D.I. Water | q.s. to 100.0 | Diluent |
| 2. STEPANQUAT ® ML1 | 2.5 | Conditioning agent, |
| emulsifier | ||
| 3. KESSCO ® PEG 600 ML2 | 0.5 | Emollient |
| PHASE B | ||
| 4. KESSCO ® Octyl Isononanoate3 | 10.0 | Emollient |
| 5. Abil EM-904 | 1.5 | Co-Emulsifier |
| 6. Parsol MCX5 | 7.5 | Organic Sunscreen |
| 7. Escalol 5876 | 5.0 | Organic Sunscreen |
| 8. Lipocol L7 | ||
| PHASE C | ||
| PHASE D | ||
| 9. Preservative, color, fragrance | q.s. | Additive |
| Properties: | ||
| Appearance | Cream | |
| pH | ||
| SPF | ||
| 1Quaternary Ammonium Compound (Stepan) | ||
| 2Polyethylene Glycol 600 Monolaurate (Stepan) | ||
| 3Octyl Isonononoate (Stepan) | ||
| 4Goldschmidt (Cetyl dimethicone copolyol) | ||
| 5Octyl methoxycinnamate (Roche Chemicals, Inc.) | ||
| 6Octyl Salicylate (ISP Van Dyk, Inc.) | ||
| 7Lauryl Alcohol (Lipo Chemicals, Inc.) | ||
Mixing Procedure
1. Prepare phase A by combining items #1, 2 and 3 at 25 C. with agitation.
2. Prepare phase B by combining items #4, 5, 6 and 7 at 25 C. with agitation.
3. Combine phase A and phase B while maintaining good agitation at about 25C. to form an intermediate batch.
4. Add phase D to the intermediate batch at 25 C. with agitation.
5. Homogenize the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
| Ingredients | % by wt. | Functionality |
| PHASE A | ||
| 1. D.I. Water | q.s. to 100.0 | Diluent |
| 2. STEPANQUAT ® ML1 | 2.5 | Conditioning agent, |
| emulsifier | ||
| 3. KESSCO ® PEG 600 ML2 | 0.5 | Emollient |
| PHASE B | ||
| 4. KESSCO ® Octyl Palmitate3 | 10.0 | Emollient |
| 5. Abil EM-904 | 1.5 | Co-Emulsifier |
| 6. Escalol 5575 | 7.5 | Organic Sunscreen |
| 7. Escalol 5876 | 5.0 | Organic Sunscreen |
| 8. Lipocol L7 | ||
| PHASE C | ||
| PHASE D | ||
| 9. Preservative, color, fragrance | q.s. | Additive |
| Properties: | ||
| Appearance | Thin emulsion! | |
| pH | ||
| SPF | ||
| 1Quaternary Ammonium Compound (Stepan) | ||
| 2Polyethylene Glycol 600 Monolaurate (Stepan) | ||
| 3Octyl Palmitate (Stepan) | ||
| 4Goldschmidt (Cetyl dimethicone copolyol) | ||
| 5Octyl methoxycinnamate (ISP Van Dyk, Inc.) | ||
| 6Octyl Salicylate (ISP Van Dyk, Inc.) | ||
| 7Lauryl Alcohol (Lipo Chemicals, Inc.) | ||
Mixing Procedure
1. Prepare phase A by combining items #1, 2 and 3 at 25 C. with agitation.
2. Prepare phase B by combining items #4, 5, 6 and 7 at 25 C. with agitation.
3. Combine phase A and phase B while maintaining good agitation at about 25C. to form an intermediate batch.
4. Add phase D to the intermediate batch at 25C. with agitation.
5. Homogenize the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
| Ingredients | % by wt. | Functionality |
| PHASE A | ||
| 1. D.I. Water | q.s. to 100.0 | Diluent |
| 2. AMMONYX ® CETAC1 | 2.5 | Conditioning agent, |
| emulsifier | ||
| 3. KESSCO ® PEG 600 ML2 | 0.5 | Emollient |
| PHASE B | ||
| 4. Silicone DC 3453 | 10.0 | Emollient |
| 5. Abil EM-904 | 1.5 | Co-Emulsifier |
| 6. Escalol 5575 | 7.5 | Organic Sunscreen |
| 7. Escalol 5876 | 5.0 | Organic Sunscreen |
| 8. Lipocol L7 | ||
| PHASE C | ||
| PHASE D | ||
| 9. Preservative, color, fragrance | q.s. | Additive |
| Properties: | ||
| Appearance | Thin emulsion | |
| pH | ||
| STABILITY | Separation in 1 | |
| hour | ||
| 1Quaternary Ammonium Compound (Stepan) | ||
| 2Polyethylene Glycol 600 Monolaurate (Stepan) | ||
| 3Octyl Palmitate (Stepan) | ||
| 4Goldschmidt (Cetyl dimethicone copolyol) | ||
| 5Octyl methoxycinnamate (ISP Van Dyk, Inc.) | ||
| 6Octyl Salicylate (ISP Van Dyk, Inc.) | ||
| 7Lauryl Alcohol (Lipo Chemicals, Inc.) | ||
Mixing Procedure
1. Prepare phase A by combining items #1, 2 and 3 at 25C. with agitation.
2. Prepare phase B by combining items #4, 5, 6 and 7 at 25C. with agitation.
3. Combine phase A and phase B while maintaining good agitation at about 25C. to form an intermediate batch.
4. Add phase D to the intermediate batch at 25C. with agitation.
5. Homogenize the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
| C | |||
| (Comparative | |||
| A | Example) | ||
| Ingredients | % by wt. | % | Functionality |
| PHASE A | |||
| 1. D.I. Water | q.s. to | q.s. to | Diluent |
| 100.0 | 100.0 | ||
| 2. STEPANQUAT ® ML1 | 2.5 | — | Conditioning |
| agent, | |||
| emulsifier | |||
| 3. AMMONYX CETAC ®2 | 2.5 | 2.5 | Conditioning |
| agent, | |||
| emulsifier | |||
| 4. Glycerin3 | 4.0 | 4.0 | Humectant |
| PHASE B | |||
| 5. Varisoft T-1004 | — | 2.5 | Emulsifier/ |
| Conditioning | |||
| Agent | |||
| 6. KESSCO ® IPP5 | 3.0 | 3.0 | Emollient |
| 1. White Fonoline | 4.0 | 4.0 | Emollient |
| (Petrolatum)6 | |||
| 2. DC Silicone 2007 (350 cps) | 0.25 | 0.25 | Emollient |
| 9. KESSCO ® Cetyl | 2.0 | 2.0 | Bodifying |
| Alcohol8 | Agent | ||
| PHASE C | |||
| PHASE D | |||
| 10. Preservative, color, | q.s. | q.s. | Additive |
| fragrance | |||
| Properties: | |||
| Appearance | Lotion | Lotion | |
| 1Quaternary Ammonium Compound (Stepan) | |||
| 2Cetrimonium Chloride (Stepan) | |||
| 3Glycerol (J.T. Baker) | |||
| 4Dimethyl Distearyl Ammonium Chloride (Sherex) | |||
| 5Isopropyl Palmitate (Stepan) | |||
| 6Petrolatum (Witco) | |||
| 7Dimethicone (Dow Corning) | |||
| 8Cetyl Alcohol (Stepan Co.) | |||
Mixing Procedure
1. Prepare phase A by combining items #1,2, 3 and 4 at 25C. with agitation.
2. Heat to phase A to 70-75 F.
3. Prepare phase B by adding items #5, 6, 7 and 8 at 25C. with agitation.
4. Heat phase B to 70-75 F.
5. Combine phase A and phase B while maintaining good agitation at 70-75 F. to form an intermediate batch.
6. Continue mixing the intermediate batch at 70-75 F. for 20-25 minutes.
7. Cool the intermediate batch to 30-35 F.
8. Add phase D to the intermediate batch at 30-35 F. with agitation to form a main batch.
9. Cool the main batch to about 25 C.
10. Homogenize the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
| Ingredients | % by wt. | Functionality |
| PHASE A | ||
| 1. D.I. Water | q.s. to 100.0 | Diluent |
| 2. STEPANQUAT ® ML1 | 2.0 | Conditioning |
| agent, | ||
| emulsifier | ||
| 3. KESSCO ® PEG 600 ML2 | 0.5 | Emollient |
| PHASE B | ||
| 4. KESSCO ® Octyl Isononanoate3 | 20.0 | Emollient |
| PHASE C | ||
| PHASE D | ||
| 5. Preservative, color, fragrance | q.s. | Additive |
| Properties: | ||
| Appearance | Thin emulsion | |
| 1Quaternary Ammonium Compound (Stepan) | ||
| 2Polyethylene Glycol 600 Monolaurate (Stepan) | ||
| 3Octyl Isononanoate (Stepan) | ||
Mixing Procedure
1. Prepare phase A by combining items #1, 2 and 3 at 25 C. with agitation.
2. Combine phase A and phase B while maintaining good agitation at about 25 C. to form an intermediate batch.
3. Add phase D to the intermediate batch at 25 C. with agitation.
4. Homogenizef the entire mixture for 3-5 minutes at 5000 rpm using Silverson mixer, Model #L4RT.
The invention and the manner and process of making and using it, are now described in such full, clear, concise and exact terms as to enable any person skilled in the art to which it pertains, to make and use the same. It is to be understood that the foregoing describes preferred embodiments of the present invention and that modifications may be made therein without departing from the spirit or scope of the present invention as set forth in the claims. To particularly point out and distinctly claim the subject matter regarded as invention, the following claims conclude this specification.
Claims (28)
1. A cold-mix water-in-oil emulsion comprising:
(a) from about 10% to about 50% by weight of an emollient;
(b) from about 0.5% to about 30% by weight of an emulsification system comprising a low HLB emulsifier of the formula:
where R is substantially linear nor-oleyl;
(c) from about 0% to about 35% of a co-emulsifier; and
(d) water;
the emulsification system and co-emulsifier substantially permanently maintaining the water and emollient as an emulsion, the emulsion capable of being substantially completely emulsified and stable at about 25° C.
2. A cold-mix water-in-oil emulsion according to claim 1 , comprising from about 10% to about 30% by weight of the emollient.
3. A cold-mix water-in-oil emulsion according to claim 1 , comprising from about 15% to about 25% by weight of the emollient.
4. A cold-mix water-in-oil emulsion according to claim 1 , comprising from about 0.5% to about 15% by weight of the low HLB emulsifier.
5. A cold-mix water-in-oil emulsion according to claim 1 , comprising from about 0.5% to about 8% by weight of the low HLB emulsifier.
6. A cold-mix water-in-oil emulsion according to claim 1 , comprising from about 1% to about 3% by weight of the low HLB emulsifier.
7. A cold-mix water-in-oil emulsion according to claim 1 , wherein the emollient is a dimethicone, a cyclomethicone, a triglyceride, an alcohol ester, an ethoxylated ester, a hydrocarbon, a natural oil or a mixture thereof.
8. A cold-mix water-in-oil emulsion according to claim 7 , wherein the hydrocarbon is mineral oil, mineral spirits, isohexadecane, or a mixture thereof.
9. A cold-mix water-in-oil emulsion according to claim 1 , wherein the emollient is a triglyceride, an alcohol ester, an ethoxylated ester, a glycol ether, a natural oil or a mixture thereof.
10. A cold-mix water-in-oil emulsion according to claim 9 , wherein the natural oil is sunflower oil, jojoba oil, sunflower oil, or a mixture thereof.
11. A cold-mix water-in-oil emulsion according to claim 1 , further comprising a water-soluble nonionic surfactant.
12. A cold-mix water-in-oil emulsion according to claim 11 , wherein the water-soluble nonionic surfactant is selected from the group consisting of polyethylene glycol laurate, polyethylene glycol dilaurate, and a mixture thereof.
13. A cold-mix water-in-oil emulsion according to claim 1 , comprising from about 0.2% to about 22.5% by weight of the co-emulsifier.
14. A cold-mix water-in-oil emulsion according to claim 1 , comprising from about 0.2% to about 12.0% by weight of the co-emulsifier.
15. A cold-mix water-in-oil emulsion according to claim 1 , comprising from about 0.4% to about 4.5% by weight of the co-emulsifier.
16. A cold-mix water-in-oil emulsion according to claim 1 , wherein the co-emulsifier is a dimethicone copolyol.
17. A cold-mix water-in-oil emulsion according to claim 16 , wherein the dimethicone copolyol is selected from the group consisting of a cyclomethicone-dimethicone copolyol mixture, lauryl dimethicone copolyol, cetyl dimethicone copolyol, cetyl dimethicone copolyol/polyglyceryl-4-isostearate/hexyl laurate, and a mixture thereof.
18. A cold-mix water-in-oil emulsion according to claim 1 , wherein the emulsification system further comprises a copolyol which is a mixture of cetyl dimethicone copolyol and lauryl dimethicone copolyol.
19. A cold-mix water-in-oil emulsion according to claim 18 , wherein the ratio of the low HLB emulsifier to the copolyol is from about 1:1.5 to about 2.5:1.
20. A cold-mix water-in-oil emulsion according to claim 1 , further comprising an alpha-hydroxy acid, a beta-hydroxy acid, or a mixture thereof.
21. A cold-mix water-in-oil emulsion according to claim 1 , further comprising a lightening agent.
22. A cold-mix water-in-oil emulsion according to claim 1 , further comprising a tanning agent.
23. A cold-mix water-in-oil emulsion according to claim 22 , wherein the tanning agent is dihydroxy acetone.
24. A cold-mix method for preparing a cold-mix water-in-oil emulsion comprising:
(a) preparing an oil phase by combining an emollient and a co-emulsifier at about 25° C.;
where R is substantially linear nor-oleyl, with water;
(c) combining the aqueous phase and the oil phase with agitation to produce an intermediate mixture;
(d) emulsifying the intermediate mixture to produce a water-in-oil emulsion which is substantially completely emulsified and stable at about 25° C.
25. A cold-mix method according to claim 24 , further comprising homogenizing the water-in-oil emulsion.
26. A cold-mix method according to claim 24 , wherein the emollient is a dimethicone, a cyclomethicone, a triglyceride, an alcohol ester, an ethoxylated ester, a hydrocarbon, a natural oil or a mixture thereof.
27. A cold-mix method according to claim 24 , wherein the emollient is a triglyceride, an alcohol ester, an ethoxylated ester, a glycol ether, a natural oil or a mixture thereof.
28. A method for providing moisturization to human skin, comprising applying to said human skin a cold-mix water-in-oil emulsion comprising:
(a) from about 10% to about 30% by weight of an emollient;
(b) from about 0.5% to about 30% by weight of an emulsification system comprising a low HLB emulsifier of the formula:
where R is substantially linear nor-oleyl;
(c) from about 0% to about 35% a co-emulsifier; and
(d) water;
wherein the emulsification system and the co-emulsifier substantially permanently maintain the water and emollient as an emulsion, the emulsion capable of being substantially completely emulsified and stable at about 25° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/627,783 US6423326B1 (en) | 1999-07-30 | 2000-07-27 | Cold-mix water-in-oil emulsions comprising quaternary ammonium compounds and process for producing same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14659799P | 1999-07-30 | 1999-07-30 | |
| US09/627,783 US6423326B1 (en) | 1999-07-30 | 2000-07-27 | Cold-mix water-in-oil emulsions comprising quaternary ammonium compounds and process for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US6423326B1 true US6423326B1 (en) | 2002-07-23 |
Family
ID=22518111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/627,783 Expired - Lifetime US6423326B1 (en) | 1999-07-30 | 2000-07-27 | Cold-mix water-in-oil emulsions comprising quaternary ammonium compounds and process for producing same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6423326B1 (en) |
| EP (1) | EP1204403A4 (en) |
| AU (1) | AU6495900A (en) |
| WO (1) | WO2001008648A1 (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030108579A1 (en) * | 2001-10-25 | 2003-06-12 | L'oreal | Topical composition |
| US20030220205A1 (en) * | 2002-05-23 | 2003-11-27 | Manka John S. | Emulsified based lubricants |
| US20050169855A1 (en) * | 2004-01-19 | 2005-08-04 | Beiersdorf Ag | Cosmetic and dermatological light protection formulations |
| WO2007059091A3 (en) * | 2005-11-14 | 2008-06-19 | Tanning Res Lab Inc | High sunscreen efficiency water-in-oil emulsion |
| WO2008074634A1 (en) * | 2006-12-18 | 2008-06-26 | Aco Hud Nordic Ab | Topical formulations having reduced stinging potential |
| US20080311058A1 (en) * | 2007-06-18 | 2008-12-18 | Connopco, Inc., D/B/A Unilever | Stable high internal phase emulsions and compositions comprising the same |
| US20090156877A1 (en) * | 2007-12-17 | 2009-06-18 | M-I Llc | System and method of separating hydrocarbons |
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| US20100300967A1 (en) * | 2007-11-30 | 2010-12-02 | M-I Llc | Breaker fluids and methods of using the same |
| US20100305064A1 (en) * | 2009-05-29 | 2010-12-02 | Walsh Star M | Topical skin care compositions |
| US20130058985A1 (en) * | 2010-03-19 | 2013-03-07 | Maria Margaretha Martina Willems | Spray-Pumpable Composition Suitable for Topical Skin Application |
| US8821839B2 (en) | 2010-10-22 | 2014-09-02 | Conopco, Inc. | Compositions and methods for imparting a sunless tan with a vicinal diamine |
| US8857741B2 (en) | 2012-04-27 | 2014-10-14 | Conopco, Inc. | Topical spray composition and system for delivering the same |
| US8865245B2 (en) | 2008-12-19 | 2014-10-21 | Conopco, Inc. | Edible fat powders |
| US8865194B1 (en) | 2007-12-20 | 2014-10-21 | Theraplex Company, LLC | Reducing tackiness and greasiness of petrolatum-like materials |
| US8927045B2 (en) | 2005-02-17 | 2015-01-06 | Sandra Petronella Barendse | Process for the preparation of a spreadable dispersion |
| US8940355B2 (en) | 2003-07-17 | 2015-01-27 | Conopco, Inc. | Process for the preparation of an edible dispersion comprising oil and structuring agent |
| US8961942B2 (en) | 2011-12-13 | 2015-02-24 | Conopco, Inc. | Sunless tanning compositions with adjuvants comprising sulfur comprising moieties |
| US8974548B2 (en) | 2011-09-26 | 2015-03-10 | Conopco, Inc. | Hair composition |
| US8993035B2 (en) | 2010-12-17 | 2015-03-31 | Conopco, Inc. | Edible water in oil emulsion |
| CN106860029A (en) * | 2017-02-17 | 2017-06-20 | 苏州宝丽洁日化有限公司 | A kind of physical antibacterial wet tissue |
| US9924730B2 (en) | 2010-06-22 | 2018-03-27 | Unilever Bcs Us, Inc. | Edible fat powders |
| US10219523B2 (en) | 2010-12-17 | 2019-03-05 | Upfield Us Inc. | Process of compacting a microporous fat powder and compacted fat powder so obtained |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10154547A1 (en) * | 2001-11-07 | 2003-05-15 | Beiersdorf Ag | Thin, sprayable W / O emulsions |
| FR2873572B1 (en) * | 2004-08-02 | 2007-03-09 | Oreal | WATER-IN-OIL EMULSION COMPRISING NON-VOLATILE NON-SILICONE OIL, CATIONIC AND NON-IONIC SURFACTANTS, AND ALKYLMONOGLYCOSIDE OR ALKYLPOLYGLYCOSIDE |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7090860B2 (en) * | 2001-10-25 | 2006-08-15 | L'oreal | Topical composition |
| US20030108579A1 (en) * | 2001-10-25 | 2003-06-12 | L'oreal | Topical composition |
| US6933263B2 (en) * | 2002-05-23 | 2005-08-23 | The Lubrizol Corporation | Emulsified based lubricants |
| US20030220205A1 (en) * | 2002-05-23 | 2003-11-27 | Manka John S. | Emulsified based lubricants |
| US11278038B2 (en) | 2003-07-17 | 2022-03-22 | Upfield Europe B.V. | Process for the preparation of an edible dispersion comprising oil and structuring agent |
| US8940355B2 (en) | 2003-07-17 | 2015-01-27 | Conopco, Inc. | Process for the preparation of an edible dispersion comprising oil and structuring agent |
| US20050169855A1 (en) * | 2004-01-19 | 2005-08-04 | Beiersdorf Ag | Cosmetic and dermatological light protection formulations |
| EP1865786B2 (en) † | 2005-02-17 | 2015-10-14 | Unilever N.V. | Process for the preparation of a spreadable dispersion |
| US8927045B2 (en) | 2005-02-17 | 2015-01-06 | Sandra Petronella Barendse | Process for the preparation of a spreadable dispersion |
| US9661864B2 (en) | 2005-02-17 | 2017-05-30 | Unilever Bcs Us, Inc. | Process for the preparation of a spreadable dispersion |
| WO2007059091A3 (en) * | 2005-11-14 | 2008-06-19 | Tanning Res Lab Inc | High sunscreen efficiency water-in-oil emulsion |
| WO2008074634A1 (en) * | 2006-12-18 | 2008-06-26 | Aco Hud Nordic Ab | Topical formulations having reduced stinging potential |
| EP1941860A1 (en) * | 2006-12-18 | 2008-07-09 | ACO Hud Nordic AB | Topical formulations |
| US20080311058A1 (en) * | 2007-06-18 | 2008-12-18 | Connopco, Inc., D/B/A Unilever | Stable high internal phase emulsions and compositions comprising the same |
| WO2009073411A3 (en) * | 2007-11-30 | 2009-07-23 | Mi Llc | Emulsifier blend |
| AU2008331576B2 (en) * | 2007-11-30 | 2012-03-15 | M-I Llc | Emulsifier blend |
| US20100317549A1 (en) * | 2007-11-30 | 2010-12-16 | M-I Llc | Emulsifier blend |
| US8163676B2 (en) | 2007-11-30 | 2012-04-24 | M-I L.L.C. | Emulsifier blend |
| US8227382B2 (en) * | 2007-11-30 | 2012-07-24 | M-I L.L.C. | Breaker fluids and methods of using the same |
| US20100300967A1 (en) * | 2007-11-30 | 2010-12-02 | M-I Llc | Breaker fluids and methods of using the same |
| EA018710B1 (en) * | 2007-11-30 | 2013-10-30 | Эм-Ай ЭлЭлСи | Emulsifier blend and method of performing a downhole operation |
| US20090156877A1 (en) * | 2007-12-17 | 2009-06-18 | M-I Llc | System and method of separating hydrocarbons |
| US8158000B2 (en) | 2007-12-17 | 2012-04-17 | M-I Llc | System and method of separating hydrocarbons |
| US8865194B1 (en) | 2007-12-20 | 2014-10-21 | Theraplex Company, LLC | Reducing tackiness and greasiness of petrolatum-like materials |
| US8865245B2 (en) | 2008-12-19 | 2014-10-21 | Conopco, Inc. | Edible fat powders |
| US20100303910A1 (en) * | 2009-05-29 | 2010-12-02 | Marilyne Candolives | Topical skin care compositions |
| US20100305064A1 (en) * | 2009-05-29 | 2010-12-02 | Walsh Star M | Topical skin care compositions |
| US20130058985A1 (en) * | 2010-03-19 | 2013-03-07 | Maria Margaretha Martina Willems | Spray-Pumpable Composition Suitable for Topical Skin Application |
| US9924730B2 (en) | 2010-06-22 | 2018-03-27 | Unilever Bcs Us, Inc. | Edible fat powders |
| US8821839B2 (en) | 2010-10-22 | 2014-09-02 | Conopco, Inc. | Compositions and methods for imparting a sunless tan with a vicinal diamine |
| US8993035B2 (en) | 2010-12-17 | 2015-03-31 | Conopco, Inc. | Edible water in oil emulsion |
| US10219523B2 (en) | 2010-12-17 | 2019-03-05 | Upfield Us Inc. | Process of compacting a microporous fat powder and compacted fat powder so obtained |
| US11071307B2 (en) | 2010-12-17 | 2021-07-27 | Upfield Europe B.V. | Process of compacting a microporous fat powder and compacted powder so obtained |
| US8974548B2 (en) | 2011-09-26 | 2015-03-10 | Conopco, Inc. | Hair composition |
| US8961942B2 (en) | 2011-12-13 | 2015-02-24 | Conopco, Inc. | Sunless tanning compositions with adjuvants comprising sulfur comprising moieties |
| US8857741B2 (en) | 2012-04-27 | 2014-10-14 | Conopco, Inc. | Topical spray composition and system for delivering the same |
| US9751097B2 (en) | 2012-04-27 | 2017-09-05 | Conopco, Inc. | Topical spray composition to benefit skin |
| CN106860029A (en) * | 2017-02-17 | 2017-06-20 | 苏州宝丽洁日化有限公司 | A kind of physical antibacterial wet tissue |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1204403A4 (en) | 2005-05-11 |
| WO2001008648A1 (en) | 2001-02-08 |
| EP1204403A1 (en) | 2002-05-15 |
| AU6495900A (en) | 2001-02-19 |
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